High viscosity novel base stock lubricant extreme viscosity blends

ABSTRACT

A lubricant formulation and method of blending a lubricant formulation is disclosed. The lubricant formulation comprises at least two base stocks. The first base stock comprises a viscosity greater than 300 cSt, Kv100° C. and a tight molecular weight distribution as a function of viscosity. The second base stock comprises a viscosity less than 100 cSt, Kv100° C. The lubricant formulation provides favorable properties.

This application claims benefit of U.S. Ser. No. 60/811,207 filed Jun.6, 2006.

BACKGROUND

Oil operating temperature & efficiencies are very important to thedesigners, builders, and user of equipment which employ worm gearing. Ona relative basis, a higher percentage efficiency rating for a lubricantresults in more power (torque) being transmitted through a subjectgearbox. Since more power is being transferred through a piece ofequipment using a more efficient lubricant, less power is being wastedto friction or heat. It is desirable for lubricant to be optimized formaximum power throughput and to therefore allow for lower operatingtemperatures. Lower operating temperatures in gearboxes give rise toseveral benefits which include: lower energy consumption, longer machinelife, and longer seal life. Seal failures are one of the principlereasons for repair and down-time in rotating equipment. A decrease of 10degrees Celsius of operating temperature can double seal life andtherefore decrease overall costs of operation and ownership.

A Small Worm Gear Rig measures both dynamic operating temperature andefficiency of power throughput simultaneously. In this gear rig, asplash lubricated bronze on steel worm gear set is the gearbox designemployed. The subject worm drive gearbox, 1.75 inch centerline distance,20:1 reduction ratio, was mounted in an L-shaped test rig with highprecision torque meters on both the input and output shafts of thegearbox to measure power throughput efficiency performance based oncontrol of output torque. The output torque was controlled to 100% ofthe rated load with a service factor of 1.0. Also, gearbox sump oiltemperature was carefully monitored during operation using fourthermocouples. National Basic Sensor located at 4921 Carver Avenue inTrevose, Pa. sells J-type thermocouples that are suitable for this rigtest.

All torque and temperature data was logged every 10 seconds for a periodof 12 hours after thermal stability was attained. The efficiency wascalculated by establishing the ratio of output torque to input torque.The resulting efficiency and operational temperatures were compared forexperimental blends to that of reference oils.

In addition to temperature & efficiency, air entrainment is anotherissue in lubricating oils. All lubricating oil systems contain some air.It can be found in four phases: free air, dissolved air, entrained airand foam. Free air is trapped in a system, such as an air pocket in ahydraulic line. Dissolved air is in solution with the oil and is notvisible to the naked eye. Foam is a collection of closely packed bubblessurrounded by thin films of oil that collect on the surface of the oil.

Air entrainment is a small amount of air in the form of extremely smallbubbles (generally less than 1 mm in diameter) dispersed throughout thebulk of the oil. Agitation of lubricating oil with air in equipment,such as bearings, couplings, gears, pumps, and oil return lines, mayproduce a dispersion of finely divided air bubbles in the oil. If theresidence time in the reservoir is too short to allow the air bubbles torise to the oil surface, a mixture of air and oil will circulate throughthe lubricating oil system. This may result in an inability to maintainoil pressure (particularly with centrifugal pumps), incomplete oil filmsin bearings and gears, and poor hydraulic system performance or failure.Air entrainment is treated differently than foam, and is most often acompletely separate problem. A partial list of potential effects of airentrainment include: pump cavitation, spongy, erratic operation ofhydraulics, loss of precision control; vibrations, oil oxidation,component wear due to reduced lubricant viscosity, equipment shut downwhen low oil pressure switches trip, “micro-dieseling” due to ignitionof the bubble sheath at the high temperatures generated by compressedair bubbles, safety problems in turbines if overspeed devices do notreact quickly enough, and loss of head in centrifugal pumps.

Antifoamants, including silicone additives help produce smaller bubblesin the bulk of the oil. In stagnant systems, the combination of smallerbubbles and greater sheath density can cause serious air entrainmentproblems. Turbine oil systems with quiescent reservoirs of severalthousand gallons may have air entrainment problems with as little as ahalf a part per million silicone.

One widely used method to test air release properties of petroleum oilsis ASTM D3427-03. This test method measures the time for the entrainedair content to fall to the relatively low value of 0.2% under astandardized set of test conditions and hence permits the comparison ofthe ability of oils to separate entrained air under conditions where aseparation time is available. The significance of this test method hasnot been fully established. However, entrained air can cause sponginessand lack of sensitivity of the control of turbine and hydraulic systems.This test may not be suitable for ranking oils in applications whereresidence times are short and gas contents are high.

In the ASTM D3427 method, compressed air is blown through the test oil,which has been heated to a temperature of 25, 50, or 75° C. After theair flow is stopped, the time required for the air entrained in the oilto reduce in volume to 0.2% is usually recorded as the air release time.

Accordingly, there is a need for a lubricant that provides a consistentfavorable operating temperature and power efficiency along with airrelease properties using high viscosity base stock blends. The presentinvention satisfies this need by providing a novel combination of basestocks that give the desired performance.

SUMMARY

A novel lubricant formulation is disclosed. In one embodiment the novellubricant formulation comprises at least two base stocks The first basestock is a metallocene catalyzed PAO (poly-alpha-olefins) with aviscosity greater than 300 cSt, Kv100° C. having a molecular weightdistribution (MWD) as a function of viscosity at least 10 percent lessthan the algorithm: MWD=0.2223+1.0232*log(Kv at 100° C. in cSt). Thesecond base stock is lubricating oil with a viscosity of less than 100cSt, Kv100° C.

In a second embodiment, the novel lubricant formulation comprises atleast two base stocks. A first base stock comprising a metallocenecatalyzed PAO with a viscosity greater than 400 cSt, Kv100° C. and asecond base stock comprising an oil with a viscosity less than 60 cSt,Kv100° C.

A method for blending a novel formulation is also disclosed. The methodcomprises obtaining a first synthetic base stock lubricant. The firstbase stock having a molecular weight distribution (MWD) as a function ofviscosity at least 10 percent less than the algorithm:MWD=0.2223+1.0232*log(Kv at 100° C. in cSt). A second base stocklubricant is obtained. The second base stock lubricant has a viscosityless than 100 cSt, Kv100° C. The first and second base stock lubricantsare mixed to produce the lubricating oil.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph illustrating the molecular weight distribution of Highviscosities PAO;

FIG. 2 is a graph illustrating the improved viscosities losses orimproved shear stability as a function of the viscosity of the highviscosity metallocene catalyzed base stocks.

FIG. 3 is a graph showing the improved MSWG efficiency of gear oilsformulated with high viscosity metallocene catalyzed PAO compared to thecommercially available prior art PAO.

FIG. 4 is a graph showing the improved MSWG operating temperature ofgear oils formulated with high viscosity metallocene catalyzed PAOcompared to the commercially available prior art PAO.

FIG. 5 is a graph showing the improved air release of gear oilsformulated with high viscosity metallocene catalyzed PAO compared to thecommercially available gear oils.

FIG. 6 is a graph showing the improved pour point of gear oilsformulated with high viscosity metallocene catalyzed PAO compared to thecommercially available gear oils.

DETAILED DESCRIPTION

In this patent, unless specified otherwise, all base stock viscositiesare referred to their 100° C. kinematics viscosity in cSt as measured byASTD D445 method. The ISO viscosity classification which is typicallycited for industrial lubes of finished lubricants based on viscositiesobserved at 40° C. We have discovered novel combinations of base stocksthat provide unexpected favorable improvements in lubricatingproperties. In various embodiments these properties include favorableimprovements in shear stability, air release, pour point, temperaturecontrol, viscosity loss and energy efficiency. In U.S. ProvisionalApplication No. 60/811,273, we have discovered a novel combination ofbase stocks that provides an unexpected increase in aeration properties,shear stability and energy efficiency. In U.S. Provisional ApplicationNo. 60/811,207, we have discovered the benefits of using metallocenecatalyzed PAO compared to the prior art PAO.

In one embodiment, this novel discovery is based on wide “bi-modal” and“extreme—modal” blends of oil viscosities which are base stock viscositydifferences of at least 200 cSt, preferably at least 250 cSt, andpossibly greater than 500 cSt, respectively wherein the high viscosityis at least 300 cSt, and the low viscosity base stock is less than 60cSt. Kinematic Viscosity is determined by ASTM D-445 method by measuringthe time for a volume of liquid to flow under gravity through acalibrated glass capillary viscometer. Viscosity is typically measuredin centistokes (cSt, or mm²/s) units. The ISO viscosity classificationwhich is typically cited for industrial lubes of finished lubricantsbased on viscosities observed at 40° C. Base stock oils used to blendfinished oils, are generally described using viscosities observed at100° C.

This “bi-modal” blend of viscosities also provides a temperature benefitby lowering the lubricant temperature in gear testing by approximately10° C. This temperature drop would provide increased efficiency boostsand extended seal life.

In the past high viscosity base stocks have not been practical from someapplications due to shear stability problems resulting in viscosity lossin service due to breakdown of polymeric chains. We have discovered thatnew base stocks with low with narrow molecular weight distributionsprovide excellent shear stability. This discovery provided the abilityto utilize high viscosity base stocks in what can be described as“dumbbell”, “bi-modal” and “extreme-modal” blends.

In a preferred embodiment, the new base stocks are produced according tothe method described in U.S. Provisional Application Nos. 60/650,206.These base stocks are known as metallocene catalyzed bases stocks andare described in detail below.

Metallocene Base Stocks

In one embodiment, the metallocene catalyzed PAO (or mPAO) used for thisinvention can be a co-polymer made from at least two alpha-olefins ormore, or a homo-polymer made from a single alpha-olefin feed by ametallocene catalyst system.

This copolymer mPAO composition is made from at least two alpha-olefinsof C3 to C30 range and having monomers randomly distributed in thepolymers. It is preferred that the average carbon number is at least4.1. Advantageously, ethylene and propylene, if present in the feed, arepresent in the amount of less than 50 wt % individually or preferablyless than 50 wt % combined. The copolymers of the invention can beisotactic, atactic, syndiotactic polymers or any other form ofappropriate tacticity. These copolymers have useful lubricant propertiesincluding excellent VI, pour point, low temperature viscometrics bythemselves or as blend fluid with other lubricants or other polymers.Furthermore, these copolymers have narrow molecular weight distributionsand excellent lubricating properties.

In an embodiment, mPAO is made from the mixed feed LAOs comprising atleast two and up to 26 different linear alpha-olefins selected from C3to C30 linear alpha-olefins. In a preferred embodiment, the mixed feedLAO is obtained from an ethylene growth process using an aluminumcatalyst or a metallocene catalyst. The growth olefins comprise mostlyC6 to C18-LAO. LAOs from other process, such as the SHOP process, canalso be used.

This homo-polymer mPAO composition is made from single alpha-olefinchosing from C3 to C30 range, preferably C3 to C16, most preferably C3to C14 or C3 to C12. The homo-polymers of the invention can beisotactic, atactic, syndiotactic polymers or any combination of thesetacticity or other form of appropriate tacticity. Often the tacticitycan be carefully tailored by the polymerization catalyst andpolymerization reaction condition chosen or by the hydrogenationcondition chosen. These homo-polymers have useful lubricant propertiesincluding excellent VI, pour point, low temperature viscometrics bythemselves or as blend fluid with other lubricants or other polymers.Furthermore, these homo-polymers have narrow molecular weightdistributions and excellent lubricating properties.

In another embodiment, the alpha-olefin(s) can be chosen from anycomponent from a conventional LAO production facility or from refinery.It can be used alone to make homo-polymer or together with another LAOavailable from refinery or chemical plant, including propylene,1-butene, 1-pentene, and the like, or with 1-hexene or 1-octene madefrom dedicated production facility. In another embodiment, thealpha-olefins can be chosen from the alpha-olefins produced fromFischer-Trosch synthesis (as reported in U.S. Pat. No. 5,382,739). Forexample, C3 to C16-alpha-olefins, more preferably linear alpha-olefins,are suitable to make homo-polymers. Other combinations, such as C4 andC14-LAO; C6 and C16-LAO; C8, C10, C12-LAO; or C8 and C14-LAO; C6, C10,C14-LAO; C4 and C12-LAO, etc. are suitable to make co-polymers.

The activated metallocene catalyst can be simple metallocenes,substituted metallocenes or bridged metallocene catalysts activated orpromoted by, for instance, methylaluminoxane (MAO) or a non-coordinatinganion, such as N,N-dimethylanilinium tetrakis(perfluorophenyl)borate orother equivalent non-coordinating anion and optionally withco-activators, typically trialkylaluminum compounds.

According to the invention, a feed comprising a mixture of LAOs selectedfrom C3 to C30 LAOs or a single LAO selected from C3 to C16 LAO, iscontacted with an activated metallocene catalyst under oligomerizationconditions to provide a liquid product suitable for use in lubricantcomponents or as functional fluids. This invention is also directed to acopolymer composition made from at least two alpha-olefins of C3 to C30range and having monomers randomly distributed in the polymers. Thephrase “at least two alpha-olefins” will be understood to mean “at leasttwo different alpha-olefins” (and similarly “at least threealpha-olefins” means “at least three different alpha-olefins”, and soforth).

In preferred embodiments, the average carbon number (definedhereinbelow) of said at least two alpha-olefins in said feed is at least4.1. In another preferred embodiment, the amount of ethylene andpropylene in said feed is less than 50 wt % individually or preferablyless than 50 wt % combined. A still more preferred embodiment comprisesa feed having both of the aforementioned preferred embodiments, i.e., afeed having an average carbon number of at least 4.1 and wherein theamount of ethylene and propylene is less than 50 wt % individually.

In embodiments, the product obtained is an essentially random liquidcopolymer comprising the at least two alpha-olefins. By “essentiallyrandom” is meant that one of ordinary skill in the art would considerthe products to be random copolymer. Other characterizations ofrandomness, some of which are preferred or more preferred, are providedherein. Likewise the term “liquid” will be understood by one of ordinaryskill in the art, but more preferred characterizations of the term areprovided herein. In describing the products as “comprising” a certainnumber of alpha-olefins (at least two different alpha-olefins), one ofordinary skill in the art in possession of the present disclosure wouldunderstand that what is being described in the polymerization (oroligomerization) product incorporating said certain number ofalpha-olefin monomers. In other words, it is the product obtained bypolymerizing or oligomerizing said certain number of alpha-olefinmonomers.

This improved process employs a catalyst system comprising a metallocenecompound (Formula 1, below) together with an activator such as anon-coordinating anion (NCA) (Formula 2, below) and optionally aco-activator such as a trialkylaluminum, or with methylaluminoxane (MAO)(Formula 3, below).

The term “catalyst system” is defined herein to mean a catalystprecursor/activator pair, such as a metallocene/activator pair. When“catalyst system” is used to describe such a pair before activation, itmeans the unactivated catalyst (precatalyst) together with an activatorand, optionally, a co-activator (such as a trialkyl aluminum compound).When it is used to describe such a pair after activation, it means theactivated catalyst and the activator or other charge-balancing moiety.Furthermore, this activated “catalyst system” may optionally comprisethe co-activator and/or other charge-balancing moiety. Optionally andoften, the co-activator, such as trialkylaluminum compound, is also usedas impurity scavenger.

The metallocene is selected from one or more compounds according toFormula 1, above. In Formula 1, M is selected from Group 4 transitionmetals, preferably zirconium (Zr), hafnium (Hf) and titanium (Ti), L1and L2 are independently selected from cyclopentadienyl (“Cp”), indenyl,and fluorenyl, which may be substituted or unsubstituted, and which maybe partially hydrogenated, A can be no atom, as in many un-bridgedmetallocenes or A is an optional bridging group which if present, inpreferred embodiments is selected from dialkylsilyl, dialkylmethyl,diphenylsilyl or diphenylmethyl, ethylenyl (—CH2—CH2—), alkylethylenyl(—CR2—CR2—), where alkyl can be independently C1 to C16 alkyl radical orphenyl, tolyl, xylyl radical and the like, and wherein each of the two Xgroups, Xa and Xb, are independently selected from halides, OR(R is analkyl group, preferably selected from C1 to C5 straight or branchedchain alkyl groups), hydrogen, C1 to C16 alkyl or aryl groups,haloalkyl, and the like. Usually relatively more highly substitutedmetallocenes give higher catalyst productivity and wider productviscosity ranges and are thus often more preferred.

In another embodiment, any of the polyalpha-olefins produced hereinpreferably have a Bromine number of 1.8 or less as measured by ASTM D1159, preferably 1.7 or less, preferably 1.6 or less, preferably 1.5 orless, preferably 1.4 or less, preferably 1.3 or less, preferably 1.2 orless, preferably 1.1 or less, preferably 1.0 or less, preferably 0.5 orless, preferably 0.1 or less.

In another embodiment, any of the polyalpha-olefins produced herein arehydrogenated and have a Bromine number of 1.8 or less as measured byASTM D 1159, preferably 1.7 or less, preferably 1.6 or less, preferably1.5 or less, preferably 1.4 or less, preferably 1.3 or less, preferably1.2 or less, preferably 1.1 or less, preferably 1.0 or less, preferably0.5 or less, preferably 0.1 or less.

In another embodiment, any of the polyalpha-olefins described herein mayhave monomer units represented by the formula, in addition to the allregular 1,2-connection.

where j, k and m are each, independently, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22, n is an integer from1 to 350 (preferably 1 to 300, preferably 5 to 50) as measured by protonNMR

In another embodiment, any of the polyalpha-olefins described hereinpreferably have an Mw (weight average molecular weight) of 100,000 orless, preferably between 100 and 80,000, preferably between 250 and60,000, preferably between 280 and 50,000, preferably between 336 and40,000 g/mol.

In another embodiment, any of the polyalpha-olefins described hereinpreferably have an Mn (number average molecular weight) of 50,000 orless, preferably between 200 and 40,000, preferably between 250 and30,000, preferably between 500 and 20,000 g/mole.

In another embodiment, any of the polyalpha-olefins described hereinpreferably have a molecular weight distribution (MWD=Mw/Mn) of greaterthan 1 and less than 5, preferably less than 4, preferably less than 3,preferably less than 2.5. The MWD of mPAO is always a function of fluidviscosity. Alternately any of the polyalpha-olefins described hereinpreferably have an Mw/Mn of between 1 and 2.5, alternately between 1 and3.5, depending on fluid viscosity.

The Mw, Mn and Mz are measured by GPC method using a column for mediumto low molecular weight polymers, tetrahydrofuran as solvent andpolystyrene as calibration standard, correlated with the fluid viscosityaccording to a power equation.

In a preferred embodiment of this invention, any PAO described hereinmay have a pour point of less than 0° C. (as measured by ASTM D 97),preferably less than −10° C., preferably less than −20° C., preferablyless than −25° C., preferably less than −30° C., preferably less than−35° C., preferably less than −50°, preferably between −10 and −80° C.,preferably between −15° C. and −70° C.

In a preferred embodiment of this invention, any PAO described hereinmay have a kinematic viscosity (at 40° C. as measured by ASTM D 445)from about 4 to about 50,000 cSt, preferably from about 5 cSt to about30,000 cSt at 40° C., alternately from about 4 to about 100,000 cSt,preferably from about 6 cSt to about 50,000 cSt, preferably from about10 cSt to about 30,000 cSt at 40° C.

In another embodiment, any polyalpha-olefin described herein may have akinematic viscosity at 100° C. from about 1.5 to about 5,000 cSt,preferably from about 2 to about 3,000 cSt, preferably from about 3 cStto about 1,000 cSt, more preferably from about 4 cSt to about 1,000 cSt,and yet more preferably from about 8 cSt to about 500 cSt as measured byASTM D445. The PAOs preferably have viscosities in the range of 2 to 500cSt at 100° C. in one embodiment, and from 2 to 3000 cSt at 100° C. inanother embodiment, and from 3.2 to 300 cSt in another embodiment.Alternately, the polyalpha-olefin has a KV100 of less than 200 cSt.

In another embodiment, any polyalpha olefin described herein may have akinematic viscosity at 100° C. from 3 to 10 cSt and a flash point of150° C. or more, preferably 200° C. or more (as measured by ASTM D 56).

In another embodiment, any polyalpha olefin described herein may have adielectric constant of 2.5 or less (1 kHz at 23° C. as determined byASTM D 924).

In another embodiment, any polyalpha olefin described herein may have aspecific gravity of 0.75 to 0.96 g/cm³, preferably 0.80 to 0.94 g/cm³.

In another embodiment, any polyalpha olefin described herein may have aviscosity index (VI) of 100 or more, preferably 120 or more, preferably130 or more, alternately, form 120 to 450, alternately from 100 to 400,alternately from 120 to 380, alternately from 100 to 300, alternatelyfrom 140 to 380, alternately from 180 to 306, alternately from 252 to306, alternately the viscosity index is at least about 165, alternatelyat least about 187, alternately at least about 200, alternately at leastabout 252. For many lower viscosity fluids made from 1-decene or1-decene equivalent feeds (KV100° C. of 3 to 10 cSt), the preferred VIrange is from 100 to 180. Viscosity index is determined according toASTM Method D 2270-93 [1998].

All kinematic viscosity values reported for fluids herein are measuredat 100° C. unless otherwise noted. Dynamic viscosity can then beobtained by multiplying the measured kinematic viscosity by the densityof the liquid. The units for kinematic viscosity are in m²/s, commonlyconverted to cSt or centistokes (1 cSt=10-6 m²/s or 1 cSt=1 mm²/sec).

One embodiment is a new class of poly-alpha-olefins, which have a uniquechemical composition characterized by a high degree of linear branchesand very regular structures with some unique head-to-head connections atthe end position of the polymer chain. The polyalpha-olefins, whetherhomo-polymers or co-polymers, can be isotactic, syndiotactic or atacticpolymers, or have combination of the tacticity. The newpoly-alpha-olefins when used by themselves or blended with other fluidshave unique lubrication properties.

Another embodiment is a new class of hydrogenated poly-alpha-olefinshaving a unique composition which is characterized by a high percentageof unique head-to-head connection at the end position of the polymer andby a reduced degree tacticity compared to the product beforehydrogenation. The new poly-alpha-olefins when used by itself or blendedwith another fluid have unique lubrication properties.

This improved process to produce these polymers employs metallocenecatalysts together with one or more activators (such as an alumoxane ora non-coordinating anion) and optionally with co-activators such astrialkylaluminum compounds. The metallocene catalyst can be a bridged orunbridged, substituted or unsubstituted cyclopentadienyl, indenyl orfluorenyl compound. One preferred class of catalysts are highlysubstituted metallocenes that give high catalyst productivity and higherproduct viscosity. Another preferred class of metallocenes are bridgedand substituted cyclopentadienes. Another preferred class ofmetallocenes are bridged and substituted indenes or fluorenes. Oneaspect of the processes described herein also includes treatment of thefeed olefins to remove catalyst poisons, such as peroxides, oxygen,sulfur, nitrogen-containing organic compounds, and or acetyleniccompounds. This treatment is believed to increase catalyst productivity,typically more than 5 fold, preferably more than 10 fold.

A preferred embodiment is a process to produce a polyalpha-olefincomprising:

1) contacting at least one alpha-olefin monomer having 3 to 30 carbonatoms with a metallocene compound and an activator under polymerizationconditions wherein hydrogen, if present, is present at a partialpressure of 200 psi (1379 kPa) or less, based upon the total pressure ofthe reactor (preferably 150 psi (1034 kPa) or less, preferably 100 psi(690 kPa) or less, preferably 50 psi (345 kPa) or less, preferably 25psi (173 kPa) or less, preferably 10 psi (69 kPa) or less (alternatelythe hydrogen, if present in the reactor at 30,000 ppm or less by weight,preferably 1,000 ppm or less preferably 750 ppm or less, preferably 500ppm or less, preferably 250 ppm or less, preferably 100 ppm or less,preferably 50 ppm or less, preferably 25 ppm or less, preferably 10 ppmor less, preferably 5 ppm or less), and wherein the alpha-olefin monomerhaving 3 to 30 carbon atoms is present at 10 volume % or more based uponthe total volume of the catalyst/activator/co-activator solutions,monomers, and any diluents or solvents present in the reaction; and

2) obtaining a polyalpha-olefin, optionally hydrogenating the PAO, andobtaining a PAO, comprising at least 50 mole % of a C3 to C30alpha-olefin monomer, wherein the polyalpha-olefin has a kinematicviscosity at 100° C. of 5000 cSt or less, and the polyalpha-olefincomprises Z mole % or more of units represented by the formula:

where j, k and m are each, independently, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22, n is an integer from1 to 350, and

An alternate embodiment is a process to produce a polyalpha-olefincomprising:

1) contacting a feed stream comprising one or at least one alpha-olefinmonomer having 3 to 30 carbon atoms with a metallocene catalyst compoundand a non-coordinating anion activator or alkylalumoxane activator, andoptionally an alkyl-aluminum compound, under polymerization conditionswherein the alpha-olefin monomer having 3 to 30 carbon atoms is presentat 10 volume % or more based upon the total volume of thecatalyst/activator/co-activator solution, monomers, and any diluents orsolvents present in the reactor and where the feed alpha-olefin, diluentor solvent stream comprises less than 300 ppm of heteroatom containingcompounds; and obtaining a polyalpha-olefin comprising at least 50 mole% of a C5 to C24 alpha-olefin monomer where the polyalpha-olefin has akinematic viscosity at 100° C. of 5000 cSt or less. Preferably,hydrogen, if present is present in the reactor at 30,000 ppm or less byweight, preferably 1,000 ppm or less preferably 750 ppm or less,preferably 500 ppm or less, preferably 250 ppm or less, preferably 100ppm or less, preferably 50 ppm or less, preferably 25 ppm or less,preferably 10 ppm or less, preferably 5 ppm or less.

An alternate embodiment is a process to produce a polyalpha-olefincomprising:

1) contacting a feed stream comprising at least one alpha-olefin monomerhaving 3 to 30 carbon atoms with a metallocene catalyst compound and anon-coordinating anion activator or alkylalumoxane activator, andoptionally an alkyl-aluminum compound, under polymerization conditionswherein the alpha-olefin monomer having 3 to 30 carbon atoms is presentat 10 volume % or more based upon the total volume of thecatalyst/activator/co-activator solution, monomers, and any diluents orsolvents present in the reactor and where the feed alpha-olefin, diluentor solvent stream comprises less than 300 ppm of heteroatom containingcompounds which; and obtaining a polyalpha-olefin comprising at least 50mole % of a C5 to C24alpha-olefin monomer where the polyalpha-olefin hasa kinematic viscosity at 100° C. of 5000 cSt or less; Alternately, inthis process described herein hydrogen, if present, is present in thereactor at 1000 ppm or less by weight, preferably 750 ppm or less,preferably 500 ppm or less, preferably 250 ppm or less, preferably 100ppm or less, preferably 50 ppm or less, preferably 25 ppm or less,preferably 10 ppm or less, preferably 5 ppm or less.

2) isolating the lube fraction polymers and then contacting this lubefraction with hydrogen under typical hydrogenation conditions withhydrogenation catalyst to give fluid with bromine number below 1.8, oralternatively, isolating the lube fraction polymers and then contactingthis lube fraction with hydrogen under more severe conditions withhydrogenation catalyst to give fluid with bromine number below 1.8 andwith reduce mole % of mm components than the unhydrogenated polymers.The hydrogen pressure for this process is usually in the range from 50psi to 3000 psi, preferably 200 to 2000 psi, preferably 500 to 1500 psi.

Molecular Weight Distribution (MWD)

Molecular weight distribution is a function of viscosity. The higher theviscosity the higher the molecular weight distribution. FIG. 1 is agraph showing the molecular weight distribution as a function ofviscosity at Kv100° C. The circles represent the prior art prior artPAO. The squares and upper triangles represent the new metallocenecatalyzed PAOs. Line 1 represents the preferred lower range of molecularweight distribution for the high viscosity metallocene catalyzed PAO.Line 3 represents preferred upper range of the molecular weightdistribution for the high viscosity metallocene catalyzed PAO.Therefore, the region bounded by lines 1 and 3 represents the preferredmolecular weight distribution region of the new metallocene catalyzedPAO. Line 2 represents the desirable and typical MWD of actualexperimental samples of the metallocene PAO made from 1-decene. Line 5represents molecular weight distribution of the prior art PAO.

Equation 1 represents the algorithm for line 5 or the average molecularweight distribution of the prior art PAO. Whereas equations 2, 3, and 4represent lines 1, 3 and 2 respectively.MWD=0.2223+1.0232*log(Kv at 100° C. in cSt)  Eq. 1MWD=0.41667+0.725*log(Kv at 100° C. in cSt)  Eq. 2MWD=0.8+0.3*log(Kv at 100° C. in cSt)  Eq. 3MWD=0.66017+0.44922*log(Kv at 100° C. in cSt)  Eq. 4

In at least one embodiment, the molecular weight distribution is atleast 10 percent less than equation 1. In a preferred embodiment themolecular weight distribution is less than equation 2 and in a mostpreferred embodiment the molecular weight distribution is less thanequation 2 and more than equation 4.

Table 1 is a table demonstrating the differences between metallocenecatalyzed PAO (“mPAO”) and current high viscosity prior art PAO(cHVI-PAO). Examples 1 to 8 in the Table 1 were prepared from differentfeed olefins using metallocene catalysts. The metallocene catalystsystem, products, process and feeds were described in patentapplications Nos. PCT/US2006/021399 and PCT/US2006/021231. The mPAOssamples in Table were made from C10, C6,12, C6 to C18, C6,10,14-LAOs.Examples 1 to 7 samples all have very narrow molecular weightdistribution (MWD). The MWD of mPAO depends on fluid viscosity as shownin FIG. 1. TABLE 1 Example No. 1 2 3 4 5 6 7 8 9 10 11 sample mPAO mPAOmPAO mPAO mPAO mPAO mPAO mPAO cHVI- cHVI- cHVI- type PAO PAO PAO FeedLAO C6/ C6- C6- C10 C6, 10, 14 C6,10,14 C10 C10 C10 C10 C10 C12 C18 C18(25/60/15%) (25/60/15%) 100° C. 150 151 540 671 460 794.35 1386.63 678.1150 300 1,000 Kv, cS 40° C. 1701 1600 6642 6900 5640 10318 16362 67431500 3100 10,000 Kv, cS VI 199 207 257 248 275 321 303 218 241 307 Pour,−33 −36 −21 −18 nd nd −12 −33 −27 −18 ° C. MWD by GPC Mw 7,409 8,08917,227 19772 16149 20273 31769 29333 8,974 12,511 32,200 MWD 1.79 2.011.90 1.98 2.35 2.18 1.914 5.50 2.39 2.54 4.79 % Visc Change by TRB Test(a) 20 hrs −0.33 −0.65 −2.66 −3.64 −4.03 −8.05 −19.32 −29.11 −7.42−18.70 −46.78 100 hrs −0.83 −0.70 −1.07 1.79 nd nd nd nd nd −21.83−51.09(a) CEC L-45-A-99 Taper Rolling Bearing/C. (20 hours) (KRL test 20hours) at SouthWest Research Institute

When Example 1 to 7 samples were subjected to tapered roller bearing(“TRB”) test, they show very low viscosity loss after 20 hours shearingor after extended 100 hours shearing (TRB). Generally, shear stabilityis a function of fluid viscosity. Lower viscosity fluids have minimalviscosity losses of less than 10%. When fluid viscosity is above 1000 cSas in Example 7, the fluid loss is approximately 19% viscosity. Example8 is a metallocene PAO with MWD of 5.5. This metallocene PAO showssignificant amount of viscosity loss at 29%.

Examples 9, 10 and 11 are comparative examples. The high viscosity PAOare made according to methods described in U.S. Pat. Nos. 4,827,064 and4,827,073. They have broad MWD and therefore poor shear stability in TRBtest.

The comparison of shear stability as a function of fluid viscosity formPAO with narrow MWD vs. cHVI-PAO is summarized in FIG. 2. This graphdemonstrates that the mPAO profile shown as line 21 has much improvedshear stability over wide viscosity range when compared to the cHVI-PAOprofile shown as line 23.

These examples demonstrated the importance of MWD effect on shearstability. Accordingly, The higher viscosity base stocks with tightermolecular weight distributions provide favorable shear stability even athigh viscosities.

Lubricant Formulation

The formulation is based on extreme modal blends of high viscositysynthetic group IV PAO. In a preferred embodiment, a High ViscosityIndex, metallocene-catalyzed PAO of greater than 300 cSt is blended witha low-viscosity base stock PAO and/or with one or more of Gr V basestocks, such as an ester, a polyalkylene glycol or an alkylatedaromatic, as a co-base for additive solubility. A detailed descriptionof suitable Gr V base stocks can be found in “Synthetics, Mineral Oilsand Bio-Based Lubricants, Chemistry and Technology” Edited by L. R.Rudnick, published by CRC Press, Taylor & Francis, 2005. The esters ofchoice are dibasic esters (such as adipate ester, ditridecyl adipate),mono-basic esters, polyol esters and phthalate esters. The alkylatedaromatics of choice are alkylbenzene, alkylated naphthalene and otheralkylated aromatics such as alkylated diphenylether, diphenylsulfide,biphenyl, etc. We have found that this unique base stock combination canimpart enhanced worm gear efficiency, improved air-release property anddecrease in operating temperature.

Also, unexpected and significant air release benefits result from thisdiscovery. Specifically, decreased air release times according to ASTM D3427. These air release benefits are manifest in a decrease of as muchas 75% of the standard release times of gear oil viscosity-gradelubricants. In addition to the above mentioned benefits, we alsodiscovered, significant improvements in low temperature performance(reduction in pour point).

In one embodiment, the lubricant oil comprises at least two base stockblends of oil. The first base stock blend comprises lubricant oil with aviscosity of over 300 cSt, and more preferably over 400 cSt, Kv100° C.Most preferably, the base stock is over 570 cSt, Kv100° C. but less than5000 cSt. The first base stock has a molecular weight distribution lessthan 10 percent of equation 1. In an even more preferred embodiment thefirst base stock is a metallocene catalyzed PAO with a viscosity of atleast 300, more preferably 400 and most preferably at least 600 cSt.

The second base stock blend comprises a lubricant oil with a viscosityof less than 60 cSt and preferably less than 40 cSt, and most preferablyless than 10 cSt. Preferably, the viscosity of the second lubricantshould be at least 1.5 cSt. Even more preferable is a viscosity ofbetween 1.7 and 40 cSt.

The air release performance enhancement of the current invention is anunexpected result since the typical performance of these very viscousoils (ISO 460) is typically an air release time to 0.2% air in the ASTMD3427 test to be 20 minutes or more. Also, the low temperatureperformance of these novel formulations shows significant improvement asdemonstrated in the ASTM D97 and D5133 data shown in Table 2. The airrelease performance enhancement of the current invention is unexpectedand novel since the typical performance of these very viscous oils (ISO460) is typically an air release time to 0.2% air in the ASTM D3427 testto be 20 minutes or more. TABLE 2 ASTM D3427 (75C) Results CommerciallyCurrent Invention availableISO 460 Air Release in Minutes ISO 460 GearOil Gear Oil Time to 0.1% air 6.9 25 Time to 0.2% air 5.2 21

Groups I, II, III, IV and V are broad categories of base oil stocksdeveloped and defined by the American Petroleum Institute (APIPublication 1509; www.API.org) to create guidelines for lubricant baseoils. Group I base stocks generally have a viscosity index of betweenabout 80 to 120 and contain greater than about 0.03% sulfur and/or lessthan about 90% saturates. Group II base stocks generally have aviscosity index of between about 80 to 120, and contain less than orequal to about 0.03% sulfur and greater than or equal to about 90%saturates. Group III stock generally has a viscosity index greater thanabout 120 and contains less than or equal to about 0.03% sulfur andgreater than about 90% saturates. Group IV includes polyalphaolefins(PAO). Group V base stocks include base stocks not included in GroupsI-IV. Table 3 summarizes properties of each of these five groups. Alldiscussion of Gr I to V base stocks can be found in “Synthetics, MineralOils and Bio-Based Lubricants, Chemistry and Technology” Edited by L. R.Rudnick, published by CRC Press, Taylor & Francis, 2005.

Group VI in Table 3 are Polyinternal olefins (“PIO”). Polyinternalolefins are long-chain hydrocarbons, typically a linear backbone withsome branching randomly attached; they are obtained by oligomerizationof internal n-olefins. The catalyst is usually a BF3 complex with aproton source that leads to a cationic polymerization, or promoted BF3or AlCl3 catalyst system. The process to produce polyinternal olefins(PIO) consists of four steps: reaction, neutralization/washing,hydrogenation and distillation. These steps are somewhat similar to PAOprocess. PIO are typically available in low viscosity grades, 4 cS, 6 cSand 8 cS. If necessary, low viscosity, 1.5 to 3.9 cS can also be madeconveniently by the BF3 process or other cationic processes. Typically,the n-olefins used as starting material are n-C12-C18 internal olefins,more preferably, n-C14-C116 olefins are used. PIO can be made with VIand pour points very similar to PAO, only slightly inferior. They can beused in engine and industrial lubricant formulations. For more detaileddiscussion, see Chapter 2, Polyinternalolefins in the book, “Synthetics,Mineral Oils, and Bio-Based Lubricants—Chemistry and Technology” Editedby Leslie R. Rudnick, p. 37-46, published by CRC Press, Taylor & FrancisGroup, 2006; or “Polyinternal Olefins” by Corsico, G.; Mattei, L.;Roselli, A.; Gommellini, Carlo. EURON, Milan, Italy. Chemical Industries(Dekker) (1999), 77(Synthetic Lubricants and High-Performance FunctionalFluids, (2nd Edition)), 53-62. Publisher: Marcel Dekker, Inc. PIO wasclassified by itself as Group VI fluid in API base stock classification.TABLE 3 Base Stock Properties Saturates Sulfur Viscosity Index Group I<90% and/or >0.03% and ≧80 and <120 Group II ≧90% and ≦0.03% and ≧80 and<120 Group III ≧90% and ≦0.03% and ≧120 Group IV Polyalphaolefins (PAO)Group V All other base oil stocks not included in Groups I, II, III, orIV Group VI Polyinternal olefins (PIO)

In a preferred embodiment, the base stocks include at least one basestock of synthetic oils and most preferably include at least one basestock of API group IV Poly Alpha Olefins. Synthetic oil for purposes ofthis application shall include all oils that are not naturally occurringmineral oils. Naturally occurring mineral oils are often referred to asAPI Group I oils.

A new type of PAO lubricant was introduced by U.S. Pat. Nos. 4,827,064and 4,827,073 (Wu). These PAO materials, which are produced by the useof a reduced valence state chromium catalyst, are olefin oligomers orpolymers which are characterized by very high viscosity indices whichgive them very desirable properties to be useful as lubricant basestocks and, with higher viscosity grades; as VI improvers. They arereferred to as High Viscosity Index PAOs or HVI-PAOs. The relatively lowmolecular weight high viscosity PAO materials were found to be useful aslubricant base stocks whereas the higher viscosity PAOs, typically withviscosities of 100 cSt or more, e.g. in the range of 100 to 1,000 cSt,were found to be very effective as viscosity index improvers forconventional PAOs and other synthetic and mineral oil derived basestocks.

Various modifications and variations of these high viscosity PAOmaterials are also described in the following U.S. patents to whichreference is made: U.S. Pat. Nos. 4,990,709; 5,254,274; 5,132,478;4,912,272; 5,264,642; 5,243,114; 5,208,403; 5,057,235; 5,104,579;4,943,383; 4,906,799. These oligomers can be briefly summarized as beingproduced by the oligomerization of 1-olefins in the presence of a metaloligomerization catalyst which is a supported metal in a reduced valencestate. The preferred catalyst comprises a reduced valence state chromiumon a silica support, prepared by the reduction of chromium using carbonmonoxide as the reducing agent. The oligomerization is carried out at atemperature selected according to the viscosity desired for theresulting oligomer, as described in U.S. Pat. Nos. 4,827,064 and4,827,073. Higher viscosity materials may be produced as described inU.S. Pat. No. 5,012,020 and U.S. Pat. No. 5,146,021 whereoligomerization temperatures below about 90° C. are used to produce thehigher molecular weight oligomers. In all cases, the oligomers, afterhydrogenation when necessary to reduce residual unsaturation, have abranching index (as defined in U.S. Pat. Nos. 4,827,064 and 4,827,073)of less than 0.19. Overall, the HVI-PAO normally have a viscosity in therange of about 12 to 5,000 cSt.

Furthermore, the HVI-PAOs generally can be characterized by one or moreof the following: C30-C1300 hydrocarbons having a branch ratio of lessthan 0.19, a weight average molecular weight of between 300 and 45,000,a number average molecular weight of between 300 and 18,000, a molecularweight distribution of between 1 and 5. Particularly preferred HVI-PAOsare fluids with 100° C. viscosity ranging from 5 to 5000 cSt. In anotherembodiment, viscosities of the HVI-PAO oligomers measured at 100° C.range from 3 centistokes (“cSt”) to 15,000 cSt. Furthermore, the fluidswith viscosity at 100° C. of 3 cSt to 5000 cSt have VI calculated byASTM method D2270 greater than 130. Usually they range from 130 to 350.The fluids all have low pour points, below −15° C.

The HVI-PAOs can further be characterized as hydrocarbon compositionscomprising the polymers or oligomers made from 1-alkenes, either byitself or in a mixture form, taken from the group consisting of C6-C201-alkenes. Examples of the feeds can be 1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, etc. or mixture of C6 to C14 1-alkenes ormixture of C6 to C20 1-alkenes, C6 and C12 1-alkenes, C6 and C141-alkenes, C6 and C16 1-alkenes, C6 and C18 1-alkenes, C8 and C101-alkenes, C8 and C12 1-alkenes, C8, C10 and C12 1-alkenes, and otherappropriate combinations.

The lube products usually are distilled to remove any low molecularweight compositions such as these boiling below 600° F., or with carbonnumber less than C20, if they are produced from the polymerizationreaction or are carried over from the starting material. Thisdistillation step usually improves the volatility of the finishedfluids. In certain special applications, or when no low boiling fractionis present in the reaction mixture, this distillation is not necessary.Thus the whole reaction product after removing any solvent or startingmaterial can be used as lube base stock or for the further treatments.

The lube fluids made directly from the polymerization or oligomerizationprocess usually have unsaturated double bonds or have olefinic molecularstructure. The amount of double bonds or unsaturation or olefiniccomponents can be measured by several methods, such as bromine number(ASTM 1159), bromine index (ASTM D2710) or other suitable analyticalmethods, such as NMR, IR, etc. The amount of the double bond or theamount of olefinic compositions depends on several factors—the degree ofpolymerization, the amount of hydrogen present during the polymerizationprocess and the amount of other promoters which participate in thetermination steps of the polymerization process, or other agents presentin the process. Usually, the amount of double bonds or the amount ofolefinic components is decreased by the higher degree of polymerization,the higher amount of hydrogen gas present in the polymerization process,or the higher amount of promoters participating in the terminationsteps.

It was known that, usually, the oxidative stability and light or UVstability of fluids improves when the amount of unsaturation doublebonds or olefinic contents is reduced. Therefore it is necessary tofurther hydrotreat the polymer if they have high degree of unsaturation.Usually, the fluids with bromine number of less than 5, as measured byASTM D1159, is suitable for high quality base stock application. Ofcourse, the lower the bromine number, the better the lube quality.Fluids with bromine number of less than 3 or 2 are common. The mostpreferred range is less than 1 or less than 0.1. The method tohydrotreat to reduce the degree of unsaturation is well known inliterature [U.S. Pat. No. 4,827,073, example 16). In some HVI-PAOproducts, the fluids made directly from the polymerization already havevery low degree of unsaturation, such as those with viscosities greaterthan 150 cSt at 100° C. They have bromine numbers less than 5 or evenbelow 2. In these cases, we can chose to use as is withouthydrotreating, or we can choose to hydrotreating to further improve thebase stock properties.

Another type of PAO, classified as Group IV base stock and usedextensively in many synthetic or partial synthetic industriallubricants, is produced by oligomerization or polymerization of linearalpha-olefins of C6 to C16 by promoted BF3 or AlCl3 catalysts. This typeof PAO is available in many viscosity grades ranging from 1.7 cS to 100cS from ExxonMobil Chemical Co.

Base stocks having a high paraffinic/naphthenic and saturation nature ofgreater than 90 weight percent can often be used advantageously incertain embodiments. Such base stocks include Group II and/or Group IIIhydroprocessed or hydrocracked base stocks, or their syntheticcounterparts such as polyalphaolefin oils, GTL or similar base oils ormixtures of similar base oils. For purposes of this applicationsynthetic bases stocks shall include Group II, Group III, group IV andGroup V base stocks.

A more specific example embodiment, is the combination of high viscositymetallocene catalyzed PAO having a molecular weight distribution (MWD)as a function of viscosity at least 10 percent less than the algorithm:[MWD=0.2223+1.0232*log(Kv at 100° C. in cSt)] with a low viscosity PolyAlpha Olefin (“PAO”) including PAOs with a viscosity of less than 6 cSt,and more preferably with a viscosity between 1.5 cSt or 4 cSt, Kv100° C.and even more preferably with a small amount of Group V base stocks,including esters, polyalkylene glycols, or alkylated aromatics. The Gr Vbase stocks can be used as an additional base stock or as a co-basestock with either the first and second base stocks for additivesolubility. The preferred ester is an alkyl adipate, a polyol ester oraromatic ester, such as phthalate ester. The preferred alkyl aromaticsare alkylbenzenes or alkylnaphthalenes. The preferred polyalkyleneglycols are liquid polymers or copolymers made from ethylene oxide,propylene oxide, butylenes oxides or higher alkylene oxides with somedegree of compatibility with PAO, other hydrocarbon fluids, GTL ormineral oils.

Gas to liquid (GTL) base stocks can also be preferentially used with thecomponents of this invention as a portion or all of the base stocks usedto formulate the finished lubricant. We have discovered, favorableimprovement when the components of this invention are added tolubricating systems comprising primarily Group II, Group III and/or GTLbase stocks compared to lesser quantities of alternate fluids.

GTL materials are materials that are derived via one or more synthesis,combination, transformation, rearrangement, and/ordegradation/deconstructive processes from gaseous carbon-containingcompounds, hydrogen-containing compounds, and/or elements as feedstockssuch as hydrogen, carbon dioxide, carbon monoxide, water, methane,ethane, ethylene, acetylene, propane, propylene, propyne, butane,butylenes, and butynes. GTL base stocks and base oils are GTL materialsof lubricating viscosity that are generally derived from hydrocarbons,for example waxy synthesized hydrocarbons, that are themselves derivedfrom simpler gaseous carbon-containing compounds, hydrogen-containingcompounds and/or elements as feedstocks. GTL base stock(s) include oilsboiling in the lube oil boiling range separated/fractionated from GTLmaterials such as by, for example, distillation or thermal diffusion,and subsequently subjected to well-known catalytic or solvent dewaxingprocesses to produce lube oils of reduced/low pour point; waxisomerates, comprising, for example, hydroisomerized or isodewaxedsynthesized hydrocarbons; hydro-isomerized or isodewaxed Fischer-Tropsch(“F-T”) material (i.e., hydrocarbons, waxy hydrocarbons, waxes andpossible analogous oxygenates); preferably hydroisomerized or isodewaxedF-T hydrocarbons or hydroisomerized or isodewaxed F-T waxes,hydroisomerized or isodewaxed synthesized waxes, or mixtures thereof.

GTL base stock(s) derived from GTL materials, especially,hydroisomerized/isodewaxed F-T material derived base stock(s), and otherhydroisomerized/isodewaxed wax derived base stock(s) are characterizedtypically as having kinematic viscosities at 100° C. of from about 2mm²/s to about 50 mm²/s, preferably from about 3 mm²/s to about 50mm²/s, more preferably from about 3.5 mm²/s to about 30 mm²/s, asexemplified by a GTL base stock derived by the isodewaxing of F-T wax,which has a kinematic viscosity of about 4 mm²/s at 100° C. and aviscosity index of about 130 or greater. The term GTL base oil/basestock and/or wax isomerate base oil/base stock as used herein and in theclaims is to be understood as embracing individual fractions of GTL basestock/base oil or wax isomerate base stock/base oil as recovered in theproduction process, mixtures of two or more GTL base stocks/base oilfractions and/or wax isomerate base stocks/base oil fractions, as wellas mixtures of one or two or more low viscosity GTL base stock(s)/baseoil fraction(s) and/or wax isomerate base stock(s)/base oil fraction(s)with one, two or more high viscosity GTL base stock(s)/base oilfraction(s) and/or wax isomerate base stock(s)/base oil fraction(s) toproduce a bi-modal blend wherein the blend exhibits a viscosity withinthe aforesaid recited range. Reference herein to Kinematic Viscosityrefers to a measurement made by ASTM method D445.

GTL base stocks and base oils derived from GTL materials, especiallyhydroisomerized/isodewaxed F-T material derived base stock(s), and otherhydroisomerized/isodewaxed wax-derived base stock(s), such as waxhydroisomerates/isodewaxates, which can be used as base stock componentsof this invention are further characterized typically as having pourpoints of about −5° C. or lower, preferably about −10° C. or lower, morepreferably about −15° C. or lower, still more preferably about −20° C.or lower, and under some conditions may have advantageous pour points ofabout −25° C. or lower, with useful pour points of about −30° C. toabout −40° C. or lower. If necessary, a separate dewaxing step may bepracticed to achieve the desired pour point. References herein to pourpoint refer to measurement made by ASTM D97 and similar automatedversions.

The GTL base stock(s) derived from GTL materials, especiallyhydroisomerized/isodewaxed F-T material derived base stock(s), and otherhydroisomerized/isodewaxed wax-derived base stock(s) which are basestock components which can be used in this invention are alsocharacterized typically as having viscosity indices of 80 or greater,preferably 100 or greater, and more preferably 120 or greater.Additionally, in certain particular instances, viscosity index of thesebase stocks may be preferably 130 or greater, more preferably 135 orgreater, and even more preferably 140 or greater. For example, GTL basestock(s) that derive from GTL materials preferably F-T materialsespecially F-T wax generally have a viscosity index of 130 or greater.References herein to viscosity index refer to ASTM method D2270.

In addition, the GTL base stock(s) are typically highly paraffinic ofgreater than 90 percent saturates) and may contain mixtures ofmonocycloparaffins and multicycloparaffins in combination withnon-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stocks and base oils typically havevery low sulfur and nitrogen content, generally containing less thanabout 10 ppm, and more typically less than about ppm of each of theseelements. The sulfur and nitrogen content of GTL base stock and base oilobtained by the hydroisomerization/isodewaxing of F-T material,especially F-T wax is essentially nil.

In a preferred embodiment, the GTL base stock(s) comprises paraffinicmaterials that consist predominantly of non-cyclic isoparaffins and onlyminor amounts of cycloparaffins. These GTL base stock(s) typicallycomprise paraffinic materials that consist of greater than 60 wt %non-cyclic isoparaffins, preferably greater than 80 wt % non-cyclicisoparaffins, more preferably greater than 85 wt % non-cyclicisoparaffins, and most preferably greater than 90 wt % non-cyclicisoparaffins.

Useful compositions of GTL base stock(s), hydroisomerized or isodewaxedF-T material derived base stock(s), and wax-derivedhydroisomerized/isodewaxed base stock(s), such as waxisomerates/isodewaxates, are recited in U.S. Pat. Nos. 6,080,301;6,090,989, and 6,165,949 for example.

We have discovered that this unique base stock combination can imparteven further favorable properties when combined with specific additivesystems. The additives include various commercially available gear oilpackages. These additive packages include a high performance series ofcomponents that include antiwear, antioxidant, defoamant, demulsifier,detergent, dispersant, metal passivation, and rust inhibition additivechemistries to deliver desired performance.

The additives may be chosen to modify various properties of thelubricating oils. For gear oils, the additives should provide thefollowing properties, antiwear protection, rust protection, micropittingprotection, friction reduction, and improved filterability. Personsskilled in the art will recognize various additives that can be chosento achieve favorable properties including favorable properties for gearoil applications.

The final lubricant should comprise a first lubricant base stock havinga viscosity of greater than 300 cSt, Kv100° C. The first lubricant basestock should comprise of at least 10 percent and no more than 70 percentof the final lubricant. Preferred range is at least 20 percent to 60percent. The second base stock having a viscosity less than 100 cStshould comprise at least 20 percent and no more than 70 percent of thefinal base stock total. The amount of Group V base stocks, such asesters, polyalkylene glycols or alkylated aromatics and/or additive canbe up to 90 percent of the final lubricant total with a proportionaldecrease in the acceptable ranges of first and second base stocks. Thepreferred range of group V, such as esters and additives is between 10and 90 percent. Sometimes, some Group I or II base stock can be used inthe formulation together with ester or alkylated aromatics or as a totalsubstitute.

In various embodiments, it will be understood that additives well knownas functional fluid additives in the art, can also be incorporated inthe functional fluid composition of the invention, in relatively smallamounts, if desired; frequently, less than about 0.001% up to about10-20% or more. In one embodiment, at least one oil additive is addedfrom the group consisting of antioxidants, stabilizers, antiwearadditives, dispersants, detergents, antifoam additives, viscosity indeximprovers, copper passivators, metal deactivators, rust inhibitors,corrosion inhibitors, pour point depressants, demulsifiers, anti-wearagents, extreme pressure additives and friction modifiers. The additiveslisted below are non-limiting examples and are not intented to limit theclaims.

Dispersants should contain the alkenyl or alkyl group R has an Mn valueof about 500 to about 5000 and an Mw/Mn ratio of about 1 to about 5. Thepreferred Mn intervals depend on the chemical nature of the agentimproving filterability. Polyolefinic polymers suitable for the reactionwith maleic anhydride or other acid materials or acid forming materials,include polymers containing a predominant quantity of C.sub.2 to C.sub.5monoolefins, for example, ethylene, propylene, butylene, isobutylene andpentene. A highly suitable polyolefinic polymer is polyisobutene. Thesuccinic anhydride preferred as a reaction substance is PIBSA, that is,polyisobutenyl succinic anhydride.

If the dispersant contains a succinimide comprising the reaction productof a succinic anhydride with a polyamine, the alkenyl or alkylsubstituent of the succinic anhydride serving as the reaction substanceconsists preferably of polymerised isobutene having an Mn value of about1200 to about 2500. More advantageously, the alkenyl or alkylsubstituent of the succinic anhydride serving as the reaction substanceconsists in a polymerised isobutene having an Mn value of about 2100 toabout 2400. If the agent improving filterability contains an ester ofsuccinic acid comprising the reaction product of a succinic anhydrideand an aliphatic polyhydric alcohol, the alkenyl or alkyl substituent ofthe succinic anhydride serving as the reaction substance consistsadvantageously of a polymerised isobutene having an Mn value of 500 to1500. In preference, a polymerised isobutene having an Mn value of 850to 1200 is used.

Amides suitable uses of amines include antiwear agents, extreme pressureadditives, friction modifiers or Dispersants. The amides which areutilized in the compositions of the present invention may be amides ofmono- or polycarboxylic acids or reactive derivatives thereof. Theamides may be characterized by a hydrocarbyl group containing from about6 to about 90 carbon atoms; each is independently hydrogen or ahydrocarbyl, aminohydrocarbyl, hydroxyhydrocarbyl or aheterocyclic-substituted hydrocarbyl group, provided that both are nothydrogen; each is, independently, a hydrocarbylene group containing upto about 10 carbon atoms; Alk is an alkylene group containing up toabout 10 carbon atoms.

The amide can be derived from a monocarboxylic acid, a hydrocarbyl groupcontaining from 6 to about 30 or 38 carbon atoms and more often will bea hydrocarbyl group derived from a fatty acid containing from 12 toabout 24 carbon atoms.

The amide is derived from a di- or tricarboxylic acid, will contain from6 to about 90 or more carbon atoms depending on the type ofpolycarboxylic acid. For example, when the amide is derived from a dimeracid, will contain from about 18 to about 44 carbon atoms or more, andamides derived from trimer acids generally will contain an average offrom about 44 to about 90 carbon atoms. Each is independently hydrogenor a hydrocarbyl, aminohydrocarbyl, hydroxyhydrocarbyl or aheterocyclic-substituted hydrocarbon group containing up to about 10carbon atoms. It may be independently heterocyclic substitutedhydrocarbyl groups wherein the heterocyclic substituent is derived frompyrrole, pyrroline, pyrrolidine, morpholine, piperazine, piperidine,pyridine, pipecoline, etc. Specific examples include methyl, ethyl,n-propyl, n-butyl, n-hexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl,amino-methyl, aminoethyl, aminopropyl, 2-ethylpyridine,1-ethylpyrrolidine, 1-ethylpiperidine, etc.

The alkyl group can be an alkylene group containing from 1 to about 10carbon atoms. Examples of such alkylene groups include, methylene,ethylene, propylene, etc. Also are hydrocarbylene groups, and inparticular, alkylene group containing up to about 10 carbon atoms.Examples of such hydrocarbylene groups include, methylene, ethylene,propylene, etc. The amide contains at least one morpholinyl group. Inone embodiment, the morpholine structure is formed as a result of thecondensation of two hydroxy groups which are attached to thehydrocarbylene groups. Typically, the amides are prepared by reacting acarboxylic acid or reactive derivative thereof with an amine whichcontains at least one >NH group.

Aliphatic monoamines include mono-aliphatic and di-aliphatic-substitutedamines wherein the aliphatic groups may be saturated or unsaturated andstraight chain or branched chain. Such amines include, for example,mono- and di-alkyl-substituted amines, mono- and dialkenyl-substitutedamines, etc. Specific examples of such monoamines include ethyl amine,diethyl amine, n-butyl amine, di-n-butyl amine, isobutyl amine, cocoamine, stearyl amine, oleyl amine, etc. An example of acycloaliphatic-substituted aliphatic amine is 2-(cyclohexyl)-ethylamine. Examples of heterocyclic-substituted aliphatic amines include2-(2-aminoethyl)-pyrrole, 2-(2-aminoethyl)-1-methylpyrrole,2-(2-aminoethyl)-1-methylpyrrolidine and 4-(2-aminoethyl)morpholine,1-(2-aminoethyl)piperazine, 1-(2-aminoethyl)piperidine,2-(2-aminoethyl)pyridine, 1-(2-aminoethyl)pyrrolidine,1-(3-aminopropyl)imidazole, 3-(2-aminopropyl)indole,4-(3-aminopropyl)morpholine, 1-(3-aminopropyl)-2-pipecoline,1-(3-aminopropyl)-2-pyrrolidinone, etc.

Cycloaliphatic monoamines are those monoamines wherein there is onecycloaliphatic substituent attached directly to the amino nitrogenthrough a carbon atom in the cyclic ring structure. Examples ofcycloaliphatic monoamines include cyclohexylamines, cyclopentylamines,cyclohexenylamines, cyclopentenylamines, N-ethyl-cyclohexylamine,dicyclohexylamines, and the like. Examples of aliphatic-substituted,aromatic-substituted, and heterocyclic-substituted cycloaliphaticmonoamines include propyl-substituted cyclohexyl-amines,phenyl-substituted cyclopentylamines, and pyranyl-substitutedcyclohexylamine.

Aromatic amines include those monoamines wherein a carbon atom of thearomatic ring structure is attached directly to the amino nitrogen. Thearomatic ring will usually be a mononuclear aromatic ring (i.e., onederived from benzene) but can include fused aromatic rings, especiallythose derived from naphthalene. Examples of aromatic monoamines includeaniline, di-(para-methylphenyl)amine, naphthylamine,N-(n-butyl)-aniline, and the like. Examples of aliphatic-substituted,cycloaliphatic-substituted, and heterocyclic-substituted aromaticmonoamines are para-ethoxy-aniline, para-dodecylaniline,cyclohexyl-substituted naphthylamine, variously substitutedphenathiazines, and thienyl-substituted aniline.

Polyamines are aliphatic, cycloaliphatic and aromatic polyaminesanalogous to the above-described monoamines except for the presencewithin their structure of additional amino nitrogens. The additionalamino nitrogens can be primary, secondary or tertiary amino nitrogens.Examples of such polyamines include N-amino-propyl-cyclohexylamines,N,N′-di-n-butyl-paraphenylene diamine, bis-(para-aminophenyl)methane,1,4-diaminocyclohexane, and the like.

The hydroxy-substituted amines contemplated are those having hydroxysubstituents bonded directly to a carbon atom other than a carbonylcarbon atom; that is, they have hydroxy groups capable of functioning asalcohols. Examples of such hydroxy-substituted amines includeethanolamine, di-(3-hydroxypropyl)-amine, 3-hydroxybutyl-amine,4-hydroxybutyl-amine, diethanolamine, di-(2-hydroxyamine,N-(hydroxypropyl)-propylamine, N-(2-methyl)-cyclohexylamine,3-hydroxycyclopentyl parahydroxyaniline, N-hydroxyethal piperazine andthe like.

In one embodiment, the amines useful in the present invention arealkylene polyamines including hydrogen, or a hydrocarbyl, aminohydrocarbyl, hydroxyhydrocarbyl or heterocyclic-substituted hydrocarbylgroup containing up to about 10 carbon atoms, Alk is an alkylene groupcontaining up to about 10 carbon atoms, and is 2 to about 10.Preferably, Alk is ethylene or propylene. Usually, a will have anaverage value of from 2 to about 7. Examples of such alkylene polyaminesinclude methylene polyamines, ethylene polyamines, butylene polyamines,propylene polyamines, pentylene polyamines, hexylene polyamines,heptylene polyamines, etc.

Alkylene polyamines include ethylene diamine, triethylene tetramine,propylene diamine, trimethylene diamine, hexamethylene diamine,decamethylene diamine, hexamethylene diamine, decamethylene diamine,octamethylene diamine, di(heptamethylene) triamine, tripropylenetetramine, tetraethylene pentamine, trimethylene diamine, pentaethylenehexamine, di(trimethylene)triamine, and the like. Higher homologs as areobtained by condensing two or more of the above-illustrated alkyleneamines are useful, as are mixtures of two or more of any of theafore-described polyamines.

Ethylene polyamines, such as those mentioned above, are especiallyuseful for reasons of cost and effectiveness. Such polyamines aredescribed in detail under the heading “Diamines and Higher Amines” inThe Encyclopedia of Chemical Technology, Second Edition, Kirk andOthmer, Volume 7, pages 27-39, Interscience Publishers, Division of JohnWiley and Sons, 1965, which is hereby incorporated by reference for thedisclosure of useful polyamines. Such compounds are prepared mostconveniently by the reaction of an alkylene chloride with ammonia or byreaction of an ethylene imine with a ring-opening reagent such asammonia, etc. These reactions result in the production of the somewhatcomplex mixtures of alkylene polyamines, including cyclic condensationproducts such as piperazines.

Other useful types of polyamine mixtures are those resulting fromstripping of the above-described polyamine mixtures. In this instance,lower molecular weight polyamines and volatile contaminants are removedfrom an alkylene polyamine mixture to leave as residue what is oftentermed “polyamine bottoms”. In general, alkylene polyamine bottoms canbe characterized as having less than 2, usually less than 1% (by weight)material boiling below about 200.degree. C. In the instance of ethylenepolyamine bottoms, which are readily available and found to be quiteuseful, the bottoms contain less than about 2% (by weight) totaldiethylene triamine (DETA) or triethylene tetramine (TETA). A typicalsample of such ethylene polyamine bottoms obtained from the Dow ChemicalCompany of Freeport, Tex. designated “E-100”. Gas chromatographyanalysis of such a sample showed it to contain about 0.93% “Light Ends”(most probably DETA), 0.72% TETA, 21.74% tetraethylene pentamine and76.61% pentaethylene hexamine and higher (by weight). These alkylenepolyamine bottoms include cyclic condensation products such aspiperazine and higher analogs of diethylene triamine, triethylenetetramine and the like.

The dispersants are selected from:

Mannich bases that are condensation reaction products of a highmolecular weight phenol, an alkylene polyamine and an aldehyde such asformaldehyde, Succinic-based dispersants that are reaction products of aolefin polymer and succinic acylating agent (acid, anhydride, ester orhalide) further reacted with an organic hydroxy compound and/or anamine, High molecular weight amides and esters such as reaction productsof a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol(such as glycerol, pentaerythritol or sorbitol). Ashless (metal-free)polymeric materials that usually contain an oil soluble high molecularweight backbone linked to a polar functional group that associates withparticles to be dispersed are typically used as dispersants. Zincacetate capped, also any treated dispersant, which include borated,cyclic carbonate, end-capped, polyalkylene maleic anhydride and thelike; mixtures of some of the above, in treat rates that range fromabout 0.1% up to 10-20% or more. Commonly used hydrocarbon backbonematerials are olefin polymers and copolymers, i.e.—ethylene, propylene,butylene, isobutylene, styrene; there may or may not be furtherfunctional groups incorporated into the backbone of the polymer, whosemolecular weight ranges from 300 tp to 5000. Polar materials such asamines, alcohols, amides or esters are attached to the backbone via abridge.

Antioxidants include sterically hindered alkyl phenols such as2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and2,6-di-tert-butyl-4-(2-octyl-3-propanoic) phenol; N,N-di(alkylphenyl)amines; and alkylated phenylene-diamines.

The antioxidant component may be a hindered phenolic antioxidant such asbutylated hydroxytoluene, suitably present in an amount of 0.01 to 5%,preferably 0.4 to 0.8%, by weight of the lubricant composition.Alternatively, or in addition, component b) may comprise an aromaticamine antioxidant such as mono-octylphenylalphanapthylamine orp,p-dioctyldiphenylamine, used singly or in admixture. The amineanti-oxidant component is suitably present in a range of from 0.01 to 5%by weight of the lubricant composition, more preferably 0.5 to 1.5%.

A sulfur-containing antioxidant may be any and every antioxidantcontaining sulfur, for example, including dialkyl thiodipropionates suchas dilauryl thiodipropionate and distearyl thiodipropionate,dialkyldithiocarbamic acid derivatives (excluding metal salts),bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide, mercaptobenzothiazole,reaction products of phosphorus pentoxide and olefins, and dicetylsulfide. Of these, preferred are dialkyl thiodipropionates such asdilauryl thiodipropionate and distearyl thiodipropionate. The amine-typeantioxidant includes, for example, monoalkyldiphenylamines such asmonooctyldiphenylamine and monononyldiphenylamine; dialkyldiphenylaminessuch as 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine,4,4′-dihexyldiphenylamine, 4,4′-diheptyldiphenylamine,4,4′-dioctyldiphenylamine and 4,4′-dinonyldiphenylamine,polyalkyldiphenylamines such as tetrabutyldiphenylamine,tetrahexyldiphenylamine, tetraoctyldiphenylamine andtetranonyldiphenylamine; and naphthylamines such as.alpha.-naphthylamine, phenyl-.alpha.-naphthylamine,butylphenyl-.alpha.-naphthylamine, pentylphenyl-.alpha.-naphthylamine,hexylphenyl-.alpha.-naphthylamine, heptylphenyl-.alpha.-naphthylamine,octylphenyl-.alpha.-naphthylamine and nonylphenyl-.alpha.-naphthylamine.Of these, preferred are dialkyldiphenylamines. The sulfur-containingantioxidant and the amine-type antioxidant are added to the base oil inan amount of from 0.01 to 5% by weight, preferably from 0.03 to 3% byweight, relative to the total weight of the composition.

The oxidation inhibitors that are particularly useful in lubecompositions of the invention are the hindered phenols (e.g.,2,6-di-(t-butyl)phenol); aromatic amines (e.g., alkylated diphenylamines); alkyl polysulfides; selenides; borates (e.g., epoxide/boricacid reaction products); phosphorodithioic acids, esters and/or salts;and the dithiocarbamate (e.g., zinc dithiocarbamates). These oxidationinhibitors as well as the oxidation inhibitors discussed above thepreferably of the invention at levels of about 0.05% to about 5%, morepreferably about 0.25 to about 2% by weight based on the total weight ofsuch compositions; with ratios of amine/phenolic to be from 1:10 to 10:1of the mixtures preferred.

The oxidation inhibitors that are also useful in lube compositions ofthe invention are chlorinated aliphatic hydrocarbons such as chlorinatedwax; organic sulfides and polysulfides such as benzyl disulfide,bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methylester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, andsulfurized terpene; phosphosulfurized hydrocarbons such as the reactionproduct of a phosphorus sulfide with turpentine or methyl oleate,phosphorus esters including principally dihydrocarbon and trihydrocarbonphosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexylphosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecylphosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl4-pentylphenyl phosphite, polypropylene (molecular weight500)-substituted phenyl phosphite, diisobutyl-substituted phenylphosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate,and barium heptylphenyl dithiocarbamate; Group II metalphosphorodithioates such as zinc dicyclohexylphosphorodithioate, zincdioctylphosphorodithioate, barium di(heptylphenyl)(phosphorodithioate,cadmium dinonylphosphorodithioate, and the reaction of phosphoruspentasulfide with an equimolar mixture of isopropyl alcohol,4-methyl-2-pentanol, and n-hexyl alcohol.

Oxidation inhibitors, organic compounds containing sulfur, nitrogen,phosphorus and some alkylphenols are also employed. Two general types ofoxidation inhibitors are those that react with the initiators, peroxyradicals, and hydroperoxides to form inactive compounds, and those thatdecompose these materials to form less active compounds. Examples arehindered (alkylated) phenols, e.g. 6-di(tert-butyl)-4-methylphenol[2,6-di(tert-butyl)-p-cresol, DBPC], and aromatic amines, e.g.N-phenyl-.alpha.-naphthalamine. These are used in turbine, circulation,and hydraulic oils that are intended for extended service.

Examples of amine-based antioxidants include dialkyldiphenylamines suchas p,p′-dioctyldiphenylamine (manufactured by the Seiko Kagaku Co. underthe trade designation “Nonflex OD-3”),p,p′-di-.alpha.-methylbenzyl-diphenylamine andN-p-butylphenyl-N-p′-octylphenylamine; monoalkyldiphenylamines such asmono-t-butyldiphenylamine, and monooctyldiphenylamine;bis(dialkylphenyl)amines such as di(2,4-diethylphenyl)amine anddi(2-ethyl-4-nonylphenyl)amine; alkylphenyl-1-naphthylamines such asoctylphenyl-1-naphthylamine and N-t-dodecylphenyl-1-naphthylamine;arylnaphthylamines such as 1-naphthylamine, phenyl-1-naphthylamine,phenyl-2-naphthylamine, N-hexylphenyl-2-naphthylamine andN-octylphenyl-2-naphthylamine, phenylenediamines such asN,N′-diisopropyl-p-phenylenediamine andN,N′-diphenyl-p-phenylenediamine, and phenothiazines such asphenothiazine (manufactured by the Hodogaya Kagaku Co.: Phenothiazine)and 3,7-dioctylphenothiazine.

Examples of sulphur-based antioxidants include dialkylsulphides such asdidodecylsulphide and dioctadecylsulphide; thiodipropionic acid esterssuch as didodecyl thiodipropionate, dioctadecyl thiodipropionate,dimyristyl thiodipropionate and dodecyloctadecyl thiodipropionate, and2-mercaptobenzimidazole.

Examples of phenol-based antioxidants include 2-t-butylphenol,2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol,2,4-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol,2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol,2,5-di-t-butylhydroquinone (manufactured by the Kawaguchi Kagaku Co.under trade designation “Antage DBH”), 2,6-di-t-butylphenol and2,6-di-t-butyl-4-alkylphenols such as 2,6-di-t-butyl-4-methylphenol and2,6-di-t-butyl-4-ethylphenol; 2,6-di-t-butyl-4-alkoxyphenols such as2,6-di-t-butyl-4-methoxyphenol and 2,6-di-t-butyl-4-ethoxyphenol,3,5-di-t-butyl-4-hydroxybenzylmercaptoocty-1 acetate,alkyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionates such asn-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured bythe Yoshitomi Seiyaku Co. under the trade designation “Yonox SS”),n-dodecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and2′-ethylhexyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate;2,6-di-t-butyl-.alpha.-dimethylamino-p-cresol,2,2′-methylenebis(4-alkyl—6-t-butylphenol) compounds such as2,2′-methylenebis(4-methyl-6-t-butylphe-nol) (manufactured by theKawaguchi Kagaku Co. under the trade designation “Antage W-400”) and2,2′-methylenebis(4-ethyl-6-t-butylphenol) (manufactured by theKawaguchi Kagaku Co. under the trade designation “Antage W-500”);bisphenols such as 4,4′-butylidenebis(3-methyl-6-t-butyl-phenol)(manufactured by the Kawaguchi Kagaku Co. under the trade designation“Antage W-300”), 4,4′-methylenebis(2,6-di-t-butylphenol) (manufacturedby Laporte Performance Chemicals under the trade designation “Ionox220AH”), 4,4′-bis(2,6-di-t-butylphenol), 2,2-(di-p-hydroxyphenyl)propane(Bisphenol A), 2,2-bis(3,5-di-t-butyl-4-h-ydroxyphenyl)propane,4,4′-cyclohexylidenebis(2,6-di-t-butylphenol), hexamethylene glycolbis[3, (3,5-di-t-butyl-4-hydroxyphenyl)propionate](manufactured by theCiba Speciality Chemicals Co. under the trade designation “IrganoxL109”), triethylene glycolbis[3-(3-t-butyl-4-hydrox-y-5-methylphenyl)propionate] (manufactured bythe Yoshitomi Seiyaku Co. under the trade designation “Tominox 917”),2,2′-thio[diethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate](manufactured by the Ciba Speciality Chemicals Co. under the tradedesignation “Irganox L115”),3,9-bis{1,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionylo-xy]ethyl}2,4,8,10-tetraoxaspiro[5,5]undecane(manufactured by the Sumitomo Kagaku Co. under the trade designation“Sumilizer GA80”) and 4,4′-thiobis(3-methyl-6-t-butylphenol)(manufactured by the Kawaguchi Kagaku Co. under the trade designation“Antage RC”), 2,2′-thiobis(4,6-di-t-butylresorcinol); polyphenols suchastetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionato]methane(manufactured by the Ciba Speciality Chemicals Co. under the tradedesignation “Irganox L101”),1,1,3-tris(2-methyl-4-hydroxy-5-t-butylpheny-1)butane (manufactured bythe Yoshitomi Seiyaku Co. under the trade designation “Yoshinox 930”),1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene(manufactured by Ciba Speciality Chemicals under the trade designation“Irganox 330”), bis[3,3′-bis(4′-hydroxy-3′-t-butylpheny-1)butyric acid]glycol ester,2-(3′,5′-di-t-butyl-4-hydroxyphenyl)-methyl—4-(2″,4″-di-t-butyl-3″-hydroxyphenyl)methyl-6-t-butylphenoland 2,6-bis(2′-hydroxy-3′-t-butyl-5′-methylbenzyl)-4-methylphenol; andphenol/aldehyde condensates such as the condensates of p-t-butylphenoland formaldehyde and the condensates of p-t-butylphenol andacetaldehyde.

Viscosity index improvers and/or the pour point depressant includepolymeric alkylmethacrylates and olefinic copolymers such as anethylene-propylene copolymer or a styrene-butadiene copolymer orpolyalkene such as PIB. Viscosity index improvers (VI improvers), highmolecular weight polymers that increase the relative viscosity of an oilat high temperatures more than they do at low temperatures. The mostcommon VI improvers are methacrylate polymers and copolymers, acrylatepolymers, olefin polymers and copolymers, and styrene-butadienecopolymers.

Other examples of the viscosity index improver include polymethacrylate,polyisobutylene, alpha-olefin polymers, alpha-olefin copolymers (e.g.,an ethylene-propylene copolymer), polyalkylstyrene, phenol condensates,naphthalene condensates, a styrenebutadiene copolymer and the like. Ofthese, polymethacrylate having a number average molecular weight of10,000 to 300,000, and alpha-olefin polymers or alpha-olefin copolymershaving a number average molecular weight of 1,000 to 30,000,particularly ethylene-alpha-olefin copolymers having a number averagemolecular weight of 1,000 to 10,000 are preferred.

The viscosity index increasing agents which can be used include, forexample, polymethacrylates and ethylene/propylene copolymers, othernon-dispersion type viscosity index increasing agents such as olefincopolymers like styrene/diene copolymers, and dispersible type viscosityindex increasing agents where a nitrogen containing monomer has beencopolymerized in such materials. These materials can be added and usedindividually or in the form of mixtures, conveniently in an amountwithin the range of from 0.05 to 20 parts by weight per 100 parts byweight of base oil.

Pour point depressors (PPD) include polymethacrylates. Commonly usedadditives such as alkylaromatic polymers and polymethacrylates areuseful for this purpose; typically the treat rates range from 0.001% to1.0%.

Detergents include calcium alkylsalicylates, calcium alkylphenates andcalcium alkarylsulfonates with alternate metal ions used such asmagnesium, barium, or sodium. Examples of the cleaning and dispersingagents which can be used include metal-based detergents such as theneutral and basic alkaline earth metal sulphonates, alkaline earth metalphenates and alkaline earth metal salicylates alkenylsuccinimide andalkenylsuccinimide esters and their borohydrides, phenates, salieniuscomplex detergents and ashless dispersing agents which have beenmodified with sulphur compounds. These agents can be added and usedindividually or in the form of mixtures, conveniently in an amountwithin the range of from 0.01 to 1 part by weight per 100 parts byweight of base oil; these can also be high TBN, low TBN, or mixtures ofhigh/low TBN.

Anti-rust additives include (short-chain) alkenyl succinic acids,partial esters thereof and nitrogen-containing derivatives thereof; andsynthetic alkarylsulfonates, such as metal dinonylnaphthalenesulfonates. Anti-rust agents include, for example, monocarboxylic acidswhich have from 8 to 30 carbon atoms, alkyl or alkenyl succinates orpartial esters thereof, hydroxy-fatty acids which have from 12 to 30carbon atoms and derivatives thereof, sarcosines which have from 8 to 24carbon atoms and derivatives thereof, amino acids and derivativesthereof, naphthenic acid and derivatives thereof, lanolin fatty acid,mercapto-fatty acids and paraffin oxides.

Particularly preferred anti-rust agents are indicated below. Examples ofMonocarboxylic Acids (C8-C30), Caprylic acid, pelargonic acid, decanoicacid, undecanoic acid, lauric acid, myristic acid, palmitic acid,stearic acid, arachic acid, behenic acid, cerotic acid, montanic acid,melissic acid, oleic acid, docosanic acid, erucic acid, eicosenic acid,beef tallow fatty acid, soy bean fatty acid, coconut oil fatty acid,linolic acid, linoleic acid, tall oil fatty acid, 12-hydroxystearicacid, laurylsarcosinic acid, myritsylsarcosinic acid, palmitylsarcosinicacid, stearylsarcosinic acid, oleylsarcosinic acid, alkylated (C8-C20)phenoxyacetic acids, lanolin fatty acid and C8-C24 mercapto-fatty acids.

Examples of Polybasic Carboxylic Acids: The alkenyl (C10—C100) succinicacids indicated in CAS No. 27859-58-1 and ester derivatives thereof,dimer acid, N-acyl-N-alkyloxyalkyl aspartic acid esters (U.S. Pat. No.5,275,749). Examples of the alkylamines which function as antirustadditives or as reaction products with the above carboxylates to giveamides and the like are represented by primary amines such aslaurylamine, coconut-amine, n-tridecylamine, myristylamine,n-pentadecylamine, palmitylamine, n-heptadecylamine, stearylamine,n-nonadecylamine, n-eicosylamine, n-heneicosylamine, n-docosylamine,n-tricosylamine, n-pentacosylamine, oleylamine, beef tallow-amine,hydrogenated beef tallow-amine and soy bean-amine. Examples of thesecondary amines include dilaurylamine, di-coconut-amine,di-n-tridecylamine, dimyristylamine, di-n-pentadecylamine,dipalmitylamine, di-n-pentadecylamine, distearylamine,di-n-nonadecylamine, di-n-eicosylamine, di-n-heneicosylamine,di-n-docosylamine, di-n-tricosylamine, di-n-pentacosyl-amine,dioleylamine, di-beef tallow-amine, di-hydrogenated beef tallow-amineand di-soy bean-amine. Examples of the aforementionedN-alkylpolyalkyenediamines include: ethylenediamines such aslaurylethylenediamine, coconut ethylenediamine,n-tridecylethylenediamine-, myristylethylenediamine,n-pentadecylethylenediamine, palmitylethylenediamine,n-heptadecylethylenediamine, stearylethylenediamine,n-nonadecylethylenediamine, n-eicosylethylenediamine,n-heneicosylethylenediamine, n-docosylethylendiamine,n-tricosylethylenediamine, n-pentacosylethylenediamine,oleylethylenediamine, beef tallow-ethylenediamine, hydrogenated beeftallow-ethylenediamine and soy bean-ethylenediamine; propylenediaminessuch as laurylpropylenediamine, coconut propylenediamine,n-tridecylpropylenediamine, myristylpropylenediamine,n-pentadecylpropylenediamine, palmitylpropylenediamine,n-heptadecylpropylenediamine, stearylpropylenediamine,n-nonadecylpropylenediamine, n-eicosylpropylenediamine,n-heneicosylpropylenediamine, n-docosylpropylendiamine,n-tricosylpropylenediamine, n-pentacosylpropylenediamine, diethylenetriamine (DETA) or triethylene tetramine (TETA), oleylpropylenediamine,beef tallow-propylenediamine, hydrogenated beef tallow-propylenediamineand soy bean-propylenediamine; butylenediamines such aslaurylbutylenediamine, coconut butylenediamine,n-tridecylbutylenediamine-, myristylbutylenediamine,n-pentadecylbutylenediamine, stearylbutylenediamine,n-eicosylbutylenediamine, n-heneicosylbutylenedia-mine,n-docosylbutylendiamine, n-tricosylbutylenediamine,n-pentacosylbutylenediamine, oleylbutylenediamine, beeftallow-butylenediamine, hydrogenated beef tallow-butylenediamine and soybean butylenediamine; and pentylenediamines such aslaurylpentylenediamine, coconut pentylenediamine,myristylpentylenediamin-e, palmitylpentylenediamine,stearylpentylenediamine, oleyl-pentylenediamine, beeftallow-pentylenediamine, hydrogenated beef tallow-pentylenediamine andsoy bean pentylenediamine.

Demulsifying agents include alkoxylated phenols and phenol-formaldehyderesins and synthetic alkylaryl sulfonates such as metallicdinonylnaphthalene sulfonates. A demulsifing agent is a predominantamount of a water-soluble polyoxyalkylene glycol having a pre-selectedmolecular weight of any value in the range of between about 450 and 5000or more. An especially preferred family of water soluble polyoxyalkyleneglycol useful in the compositions of the present invention may also beone produced from alkoxylation of n-butanol with a mixture of alkyleneoxides to form a random alkoxylated product.

Functional fluids according to the invention possess a pour point ofless than about −20 degree C., and exhibit compatibility with a widerange of anti-wear additive and extreme pressure additives. Theformulations according to the invention also are devoid of fatiguefailure that is normally expected by those of ordinary skill in the artwhen dealing with polar lubricant base stocks.

Polyoxyalkylene glycols useful in the present invention may be producedby a well-known process for preparing polyalkylene oxide having hydroxylend-groups by subjecting an alcohol or a glycol ether and one or morealkylene oxide monomers such as ethylene oxide, butylene oxide, orpropylene oxide to form block copolymers in addition polymerizationwhile employing a strong base such as potassium hydroxide as a catalyst.In such process, the polymerization is commonly carried out under acatalytic concentration of 0.3 to 1.0% by mole of potassium hydroxide tothe monomer(s) and at high temperature, as 100 degrees C. to 160 degreesC. It is well known fact that the potassium hydroxide being a catalystis for the most part bonded to the chain-end of the producedpolyalkylene oxide in a form of alkoxide in the polymer solution soobtained.

An especially preferred family of soluble polyoxyalkylene glycol usefulin the compositions of the present invention may also be one producedfrom alkoxylation of n-butanol with a mixture of alkylene oxides to forma random alkoxylated product.

Foam inhibitors include polymers of alkyl methacrylate especially usefulpoly alkyl acrylate polymers where alkyl is generally understood to bemethyl, ethyl propyl, isopropyl, butyl, or iso butyl and polymers ofdimethylsilicone which form materials called dimethylsiloxane polymersin the viscosity range of 10 cSt to 100,000 cSt. Other additives aredefoamers, such as silicone polymers which have been post reacted withvarious carbon containing moieties, are the most widely used defoamers.Organic polymers are sometimes used as defoamers although much higherconcentrations are required.

Metal deactivating compounds/Corrosion inhibitors include2,5-dimercapto-1,3,4-thiadiazoles and derivatives thereof,mercaptobenzothiazoles, alkyltriazoles and benzotriazoles. Examples ofdibasic acids useful as anti-corrosion agents, other than sebacic acids,which may be used in the present invention, are adipic acid, azelaicacid, dodecanedioic acid, 3-methyladipic acid, 3-nitrophthalic acid,1,10-decanedicarboxylic acid, and fumaric acid. The anti-corrosioncombination is a straight or branch-chained, saturated or unsaturatedmonocarboxylic acid or ester thereof which may optionally be sulphurisedin an amount up to 35% by weight. Preferably the acid is a C sub 4 to Csub 22 straight chain unsaturated monocarboxylic acid. The preferredconcentration of this additive is from 0.001% to 0.35% by weight of thetotal lubricant composition. The preferred monocarboxylic acid issulphurised oleic acid. However, other suitable materials are oleic aciditself; valeric acid and erucic acid. A component of the anti-corrosioncombination is a triazole as previously defined. The triazole should beused at a concentration from 0.005% to 0.25% by weight of the totalcomposition. The preferred triazole is tolylotriazole which may beincluded in the compositions of the invention include triazoles,thiazoles and certain diamine compounds which are useful as metaldeactivators or metal passivators. Examples include triazole,benzotriazole and substituted benzotriazoles such as alkyl substitutedderivatives. The alkyl substituent generally contains up to 1.5 carbonatoms, preferably up to 8 carbon atoms. The triazoles may contain othersubstituents on the aromatic ring such as halogens, nitro, amino,mercapto, etc. Examples of suitable compounds are benzotriazole and thetolyltriazoles, ethylbenzotriazoles, hexylbenzotriazoles,octylbenzotriazoles, chlorobenzotriazoles and nitrobenzotriazoles.Benzotriazole and tolyltriazole are particularly preferred. A straightor branched chain saturated or unsaturated monocarboxylic acid which isoptionally sulphurised in an amount which may be up to 35% by weight; oran ester of such an acid; and a triazole or alkyl derivatives thereof,or short chain alkyl of up to 5 carbon atoms; n is zero or an integerbetween 1 and 3 inclusive; and is hydrogen, morpholino, alkyl, amido,amino, hydroxy or alkyl or aryl substituted derivatives thereof; or atriazole selected from 1,2,4 triazole, 1,2,3 triazole,5-anilo-1,2,3,4-thiatriazole, 3-amino-1,2,4 triazole,1-H-benzotriazole-1-yl-methylisocyanide, methylene-bis-benzotriazole andnaphthotriazole.

Alkyl is straight or branched chain and is for example methyl, ethyl,n-propyl, iso-propyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl,n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl,n-hexadecyl, n-octadecyl or n-eicosyl.

Alkenyl is straight or branched chain and is for example prop-2-enyl,but-2-enyl, 2-methyl-prop-2-enyl, pent-2-enyl, hexa-2,4-dienyl,dec-10-enyl or eicos-2-enyl.

Cylcoalkyl is for example cyclopentyl, cyclohexyl, cyclooctyl,cyclodecyl, adamantyl or cyclododecyl.

Aralkyl is for example benzyl, 2-phenylethyl, benzhydryl ornaphthylmethyl. Aryl is for example phenyl or naphthyl.

The heterocyclic group is for example a morpholine, pyrrolidine,piperidine or a perhydroazepine ring.

Alkylene moieties include for example methylene, ethylene, 1:2- or1:3-propylene, 1:4-butylene, 1:6-hexylene, 1:8-octylene, 1:10-decyleneand 1:12-dodecylene.

Arylene moieties include for example phenylene and naphthylene. 1-(or4)-(dimethylaminomethyl) triazole, 1-(or 4)-(diethylaminomethyl)triazole, 1-(or 4)-(di-isopropylaminomethyl) triazole, 1-(or4)-(di-n-butylaminomethyl) triazole, 1-(or 4)-(di-n-hexylaminomethyl)triazole, 1-(or 4)-(di-isooctylaminomethyl) triazole, 1-(or4)-(di-(2-ethylhexyl)aminomethyl) triazole, 1-(or4)-(di-n-decylaminomethyl) triazole, 1-(or 4)-(di-n-dodecylaminomethyl)triazole, 1-(or 4)-(di-n-octadecylaminomethyl) triazole, 1-(or4)-(di-n-eicosylaminomethyl) triazole, 1-(or4)-[di-(prop-2′-enyl)aminomethyl] triazole, 1-(or4)-[di-(but-2′-enyl)aminomethyl] triazole, 1-(or4)-[di-(eicos-2′-enyl)aminomethyl] triazole, 1-(or4)-(di-cyclohexylaminomethyl) triazole, 1-(or 4)-(di-benzylaminomethyl)triazole, 1-(or 4)-(di-phenylaminomethyl) triazole, 1-(or4)-(4′-morpholinomethyl) triazole, 1-(or 4)-(1′-pyrrolidinomethyl)triazole, 1-(or 4)-(1′-piperidinomethyl) triazole, 1-(or4)-(1′-perhydroroazepinomethyl) triazole, 1-(or4)-(2′,2″-dihydroxyethyl)aminomethyl] triazole, 1-(or4)-(dibutoxypropyl-aminomethyl) triazole, 1-(or4)-(dibutylthiopropyl-aminomethyl) triazole, 1-(or4)-(di-butylaminopropyl-aminomethyl) triazole, 1-(or-4)-(1-methanomine)-N,N-bis(2-ethylhexyl)-methyl benzotriazole,N,N-bis-(1- or 4-triazolylmethyl) laurylamine, N,N-bis-(1- or4-triazolylmethyl) oleylamine, N,N-bis-(1- or4-triazolylmethyl)ethanolamine and N,N,N′,N′-tetra(1- or4-triazolylmethyl)ethylene diamine.

Also, dihydrocarbyl dithiophosphate metal salts where the metal isaluminum, lead, tin, manganese, molybedenum, antimony, cobalt, nickel,zinc or copper, but most often zinc. Sulfur- and/or phosphorus- and/orhalogen-containing compounds, such as sulfurized olefins and vegetableoils, tritolyl phosphate, tricresyl phosphate, chlorinated paraffins,alkyl and aryl di- and trisulfides, amine salts of mono- and dialkylphosphates, amine salts of methylphosphonic acid,diethanolaminomethyltolyltriazole,di(2-ethylhexyl)-aminomethyltolyltriazole, derivatives of2,5-dimercapto-1,3,4-thiadiazole, ethyl((bisisopropyloxyphosphinothioyl)-thio)propionate, triphenylthiophosphate (triphenyl phosphorothioate), tris(alkylphenyl)phosphorothioates and mixtures thereof (for example tris(isononylphenyl)phosphorothioate), diphenylmonononylphenyl phosphorothioate,isobutylphenyl diphenyl phosphorothioate, the dodecylamine salt of3-hydroxy-1,3-thiaphosphetan 3-oxide, trithiophosphoric acid5,5,5-tris(isooctyl 2-acetate), derivatives of 2-mercaptobenzothiazole,such as1-(N,N-bis(2-ethylhexyl)aminomethyl)-2-m-ercapto-1H-1,3-benzothiazole orethoxycarbonyl 5-octyldithiocarbamate.

The metal deactivating agents which can be used in the lubricating oil acomposition of the present invention include benzotriazole and the4-alkylbenzotriazoles such as 4-methylbenzotriazole and4-ethylbenzotriazole; 5-alkylbenzotriazoles such as5-methylbenzotriazole, 5-ethylbenzotriazole; 1-alkylbenzotriazoles suchas 1-dioctylauainomethyl-2,3-benzotriazole; benzotriazole derivativessuch as the 1-alkyltolutriazoles, for example,1-dioctylaminomethyl-2,3-t-olutriazole; benzimidazole and benzimidazolederivatives such as 2-(alkyldithio)-benzimidazoles, for example, such as2-(octyldithio)-benzimidazole, 2-(decyldithio)benzimidazole and2-(dodecyldithio)-benzimidazole; 2-(alkyldithio)-toluimidazoles such as2-(octyldithio)-toluimidazole, 2-(decyldithio)-toluimidazole and2-(dodecyldithio)-toluimidazole; indazole and indazole derivatives oftoluimidazoles such as 4-alkylindazole, 5-alkylindazole; benzothiazole,2-mercaptobenzothiazole derivatives (manufactured by the Chiyoda KagakuCo. under the trade designation “Thiolite B-3100”) and2-(alkyldithio)benzothiazoles such as 2-(hexyldithio)benzothiazole and2-(octyldithio)benzothiazole; 2-(alkyl-dithio)toluthiazoles such as2-(benzyldithio)toluthiazole and 2-(octyldithio)toluthiazole,2-(N,N-dialkyldithiocarbamyl)benzothiazoles such as2-(N,N-diethyldithiocarbamyl)benzothiazole,2-(N,N-dibutyldithiocarbamyl)-benzotriazole and2-N,N-dihexyl-dithiocarbamyl)benzotriazole; benzothiazole derivatives of2-(N,N-dialkyldithiocarbamyl)toluthiazoles such as2-(N,N-diethyldithiocarbamyl)toluthiazole,2-(N,N-dibutyldithiocarbamyl)toluthiazole,2-(N,N-dihexyl-dithiocarbamyl)-toluthiazole; 2-(alkyldithio)benzoxazolessuch as 2-(octyldithio)benzoxazo-le, 2-(decyldithio)-benzoxazole and2-(dodecyldithio)benzoxazole; benzoxazole derivatives of2-(alkyldithio)toluoxazoles such as 2-(octyldithio)toluoxazole,2-(decyldithio)toluoxazole, 2-(dodecyldithio)toluoxazole;2,5-bis(alkyldithio)-1,3,4-thiadiazoles such as2,5-bis(heptyldithio)-1,3,4-thiadiazole, 2,5-bis-(nonyldithio)-1,-3,4-thiadiazole, 2,5-bis(dodecyldithio)-1,3,4-thiadiazole and2,5-bis-(octadecyldithio)-1,3,4-thiadiazole;2,5-bis(N,N-dialkyl-dithiocarbamyl)-1,3,4-thiadiazoles such as2,5-bis(N,N-diethyldithiocarbamyl)-1,3,-4-thiadiazole,2,5-bis(N,N-dibutyldithiocarbamyl)-1,3,4-thiadiazole and2,5-bis(N,N-dioctyldithiocarbamyl)1,3,4-thiadiazole; thiadiazolederivatives of 2-N,N-dialkyldithiocarbamyl-5-mercapto-1,3,4-thiadiazolessuch as 2-N,N-dibutyldithiocarbamyl-5-mercapto-1,3,4-thiadiazole and2-N,N-dioctyl-dithiocarbamyl-5-mercapto-1,3,4-thiadiazole, and triazolederivatives of 1-alkyl-2,4-triazoles such as1-dioctylaminomethyl-2,4-tri-azole or concentrates and/or mixturesthereof.

Anti-wear agents/Extreme pressure agent/Friction Reducer: zincalkyldithiophosphates, aryl phosphates and phosphites, sulfur-containingesters, phosphosulfur compounds, and metal or ash-free dithiocarbamates.

A phosphate ester or salt may be a monohydrocarbyl, dihydrocarbyl or atrihydrocarbyl phosphate, wherein each hydrocarbyl group is saturated.In one embodiment, each hydrocarbyl group independently contains fromabout 8 to about 30, or from about 12 up to about 28, or from about 14up to about 24, or from about 14 up to about 18 carbons atoms. In oneembodiment, the hydrocarbyl groups are alkyl groups. Examples ofhydrocarbyl groups include tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl groups and mixtures thereof.

A phosphate ester or salt is a phosphorus acid ester prepared byreacting one or more phosphorus acid or anhydride with a saturatedalcohol. The phosphorus acid or anhydride is generally an inorganicphosphorus reagent, such as phosphorus pentoxide, phosphorus trioxide,phosphorus tetroxide, phosphorous acid, phosphoric acid, phosphorushalide, lower phosphorus esters, or a phosphorus sulfide, includingphosphorus pentasulfide, and the like. Lower phosphorus acid estersgenerally contain from 1 to about 7 carbon atoms in each ester group.Alcohols used to prepare the phosphorus acid esters or salts. Examplesof commercially available alcohols and alcohol mixtures include Alfol1218 (a mixture of synthetic, primary, straight-chain alcoholscontaining 12 to 18 carbon atoms); Alfol 20+ alcohols (mixtures of C18-C 28 primary alcohols having mostly C20 alcohols as determined by GLC(gas-liquid-chromatography)); and Alfol22+ alcohols (C 18-C 28 primaryalcohols containing primarily C 22 alcohols). Alfol alcohols areavailable from Continental Oil Company. Another example of acommercially available alcohol mixture is Adol 60 (about 75% by weightof a straight chain C 22 primary alcohol, about 15% of a C 20 primaryalcohol and about 8% of C 18 and C 24 alcohols). The Adol alcohols aremarketed by Ashland Chemical.

A variety of mixtures of monohydric fatty alcohols derived fromnaturally occurring triglycerides and ranging in chain length from C 8to C 18 are available from Procter & Gamble Company. These mixturescontain various amounts of fatty alcohols containing 12, 14, 16, or 18carbon atoms. For example, CO-1214 is a fatty alcohol mixture containing0.5% of C 10 alcohol, 66.0% of C 12 alcohol, 26.0% of C 14 alcohol and6.5% of C 16 alcohol.

Another group of commercially available mixtures include the “Neodol”products available from Shell Chemical Co. For example, Neodol 23 is amixture of C 12 and C 13 alcohols; Neodol 25 is a mixture of C 12 to C15 alcohols; and Neodol 45 is a mixture of C 14 to C 15 linear alcohols.The phosphate contains from about 14 to about 18 carbon atoms in eachhydrocarbyl group. The hydrocarbyl groups of the phosphate are generallyderived from a mixture of fatty alcohols having from about 14 up toabout 18 carbon atoms. The hydrocarbyl phosphate may also be derivedfrom a fatty vicinal diol. Fatty vicinal diols include those availablefrom Ashland Oil under the general trade designation Adol 114 and Adol158. The former is derived from a straight chain alpha olefin fractionof C 11-C 14, and the latter is derived from a C 15-C 18 fraction.

The phosphate salts may be prepared by reacting an acidic phosphateester with an amine compound or a metallic base to form an amine or ametal salt. The amines may be monoamines or polyamines. Useful aminesinclude those amines disclosed in U.S. Pat. No. 4,234,435.

The monoamines generally contain a hydrocarbyl group which contains from1 to about 30 carbon atoms, or from 1 to about 12, or from 1 to about 6.Examples of primary monoamines useful in the present invention includemethylamine, ethylamine, propylamine, butylamine, cyclopentylamine,cyclohexylamine, octylamine, dodecylamine, allylamine, cocoamine,stearylamine, and laurylamine. Examples of secondary monoamines includedimethylamine, diethylamine, dipropylamine, dibutylamine,dicyclopentylamine, dicyclohexylamine, methylbutylamine,ethylhexylamine, etc.

An amine is a fatty (C.sub.8-30) amine which includes n-octylamine,n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine,n-octadecylamine, oleyamine, etc. Also useful fatty amines includecommercially available fatty amines such as “Armeen” amines (productsavailable from Akzo Chemicals, Chicago, Ill.), such Armeen C, Armeen O,Armeen O L, Armeen T, Armeen H T, Armeen S and Armeen S D, wherein theletter designation relates to the fatty group, such as coco, oleyl,tallow, or stearyl groups.

Other useful amines include primary ether amines, such as thoserepresented by the formula, R″ (OR′)xNH 2, wherein R′ is a divalentalkylene group having about 2 to about 6 carbon atoms; x is a numberfrom one to about 150, or from about one to about five, or one; and R″is a hydrocarbyl group of about 5 to about 150 carbon atoms. An exampleof an ether amine is available under the name SURFAM® amines producedand marketed by Mars Chemical Company, Atlanta, Ga. Preferredetheramines are exemplified by those identified as SURFAM P14B(decyloxypropylamine), SURFAM P16A (linear C 16), SURFAM P17B(tridecyloxypropylamine). The carbon chain lengths (i.e., C 14, etc.) ofthe SURFAMS described above and used hereinafter are approximate andinclude the oxygen ether linkage.

An amine is a tertiary-aliphatic primary amine. Generally, the aliphaticgroup, preferably an alkyl group, contains from about 4 to about 30, orfrom about 6 to about 24, or from about 8 to about 22 carbon atoms.Usually the tertiary alkyl primary amines are monoamines the alkyl groupis a hydrocarbyl group containing from one to about 27 carbon atoms andR 6 is a hydrocarbyl group containing from 1 to about 12 carbon atoms.Such amines are illustrated by tert-butylamine, tert-hexylamine,1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine,tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine,tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine.Mixtures of tertiary aliphatic amines may also be used in preparing thephosphate salt. Illustrative of amine mixtures of this type are “Primene81R” which is a mixture of C 11-C 14 tertiary alkyl primary amines and“Primene JMT” which is a similar mixture of C 18-C 22 tertiary alkylprimary amines (both are available from Rohm and Haas Company). Thetertiary aliphatic primary amines and methods for their preparation areknown to those of ordinary skill in the art. The tertiary aliphaticprimary amine useful for the purposes of this invention and methods fortheir preparation are described in U.S. patent. An amine is aheterocyclic polyamine. The heterocyclic polyamines include aziridines,azetidines, azolidines, tetra- and dihydropyridines, pyrroles, indoles,piperidines, imidazoles, di- and tetra-hydroimidazoles, piperazines,isoindoles, purines, morpholines, thiomorpholines,N-aminoalkylmorpholines, N-aminoalkylthiomorpholines,N-aminoalkyl-piperazines, N,N′-diaminoalkylpiperazines, azepines,azocines, azonines, azecines and tetra-, di- and perhydro derivatives ofeach of the above and mixtures of two or more of these heterocyclicamines. Preferred heterocyclic amines are the saturated 5- and6-membered heterocyclic amines containing only nitrogen, oxygen and/orsulfur in the hetero ring, especially the piperidines, piperazines,thiomorpholines, morpholines, pyrrolidines, and the like. Piperidine,aminoalkyl substituted piperidines, piperazine, aminoalkyl substitutedpiperazines, morpholine, aminoalkyl substituted morpholines,pyrrolidine, and aminoalkyl-substituted pyrrolidines, are especiallypreferred. Usually the aminoalkyl substituents are substituted on anitrogen atom forming part of the hetero ring. Specific examples of suchheterocyclic amines include N-aminopropylmorpholine,N-aminoethylpiperazine, and N,N′-diaminoethylpiperazine. Hydroxyheterocyclic polyamines are also useful. Examples includeN-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine,parahydroxyaniline, N-hydroxyethylpiperazine, and the like.

The metal salts of the phosphorus acid esters are prepared by thereaction of a metal base with the acidic phosphorus ester. The metalbase may be any metal compound capable of forming a metal salt. Examplesof metal bases include metal oxides, hydroxides, carbonates, sulfates,borates, or the like. The metals of the metal base include Group IA,IIA, IB through VIIB, and VIII metals (CAS version of the Periodic Tableof the Elements). These metals include the alkali metals, alkaline earthmetals and transition metals. In one embodiment, the metal is a GroupIIA metal, such as calcium or magnesium, Group IIB metal, such as zinc,or a Group VIIB metal, such as manganese. Preferably, the metal ismagnesium, calcium, manganese or zinc. Examples of metal compounds whichmay be reacted with the phosphorus acid include zinc hydroxide, zincoxide, copper hydroxide, copper oxide, etc.

Lubricating compositions also may include a fatty imidazoline or areaction product of a fatty carboxylic acid and at least one polyamine.The fatty imidazoline has fatty substituents containing from 8 to about30, or from about 12 to about 24 carbon atoms. The substituent may besaturated or unsaturated for example, heptadeceneyl derived olyelgroups, preferably saturated. In one aspect, the fatty imidazoline maybe prepared by reacting a fatty carboxylic acid with apolyalkylenepolyamine, such as those discussed above. The fattycarboxylic acids are generally mixtures of straight and branched chainfatty carboxylic acids containing about 8 to about 30 carbon atoms, orfrom about 12 to about 24, or from about 16 to about 18. Carboxylicacids include the polycarboxylic acids or carboxylic acids or anhydrideshaving from 2 to about 4 carbonyl groups, preferably 2. Thepolycarboxylic acids include succinic acids and anhydrides andDiels-Alder reaction products of unsaturated monocarboxylic acids withunsaturated carboxylic acids (such as acrylic, methacrylic, maleic,fumaric, crotonic and itaconic acids). Preferably, the fatty carboxylicacids are fatty monocarboxylic acids, having from about 8 to about 30,preferably about 12 to about 24 carbon atoms, such as octanoic, oleic,stearic, linoleic, dodecanoic, and tall oil acids, preferably stearicacid. The fatty carboxylic acid is reacted with at least one polyamine.The polyamines may be aliphatic, cycloaliphatic, heterocyclic oraromatic. Examples of the polyamines include alkylene polyamines andheterocyclic polyamines.

Hydroxyalkyl groups are to be understood as meaning, for example,monoethanolamine, diethanolamine or triethanolamine, and the term aminealso includes diamine. The amine used for the neutralization depends onthe phosphoric esters used. The EP additive according to the inventionhas the following advantages: It very high effectiveness when used inlow concentrations and it is free of chlorine. For the neutralization ofthe phosphoric esters, the latter are taken and the corresponding amineslowly added with stirring. The resulting heat of neutralization isremoved by cooling. The EP additive according to the invention can beincorporated into the respective base liquid with the aid of fattysubstances (e.g. tall oil fatty acid, oleic acid, etc.) as solubilizers.The base liquids used are napthenic or paraffinic base oils, syntheticoils (e.g. polyglycols, mixed polyglycols), polyolefins, carboxylicesters, etc.

The composition comprises at least one phosphorus containing extremepressure additive. Examples of such additives are amine phosphateextreme pressure additives such as that known under the trade nameIRGALUBE 349 and/or triphenyl phosphorothionate extremepressure/anti-wear additives such as that known under the trade nameIRGALUBE TPPT. Such amine phosphates are suitably present in an amountof from 0.01 to 2%, preferably 0.2 to 0.6% by weight of the lubricantcomposition while such phosphorothionates are suitably present in anamount of from 0.01 to 3%, preferably 0.5 to 1.5% by weight of thelubricant composition. A mixture of an amine phosphate andphosphorothionate is employed.

At least one straight and/or branched chain saturated or unsaturatedmonocarboxylic acid which is optionally sulphurised in an amount whichmay be up to 35% by weight; and/or an ester of such an acid. At leastone triazole or alkyl derivatives thereof, or short chain alkyl of up to5 carbon atoms and is hydrogen, morphilino, alkyl, amido, amino, hydroxyor alkyl or aryl substituted derivatives thereof; or a triazole selectedfrom 1,2,4 triazole, 1,2,3 triazole, 5-anilo-1,2,3,4-thiatriazole,3-amino-1,2,4 triazole, 1-H-benzotriazole-1-yl-methylisocyanide,methylene-bis-benzotriazole and naphthotriazole; and The neutral organicphosphate which forms a component of the formulation may be present inan amount of 0.01 to 4%, preferably 1.5 to 2.5% by weight of thecomposition. The above amine phosphates and any of the aforementionedbenzo- or tolyltriazoles can be mixed together to form a singlecomponent capable of delivering antiwear performance. The neutralorganic phosphate is also a conventional ingredient of lubricatingcompositions and any such neutral organic phosphate falling within theformula as previously defined may be employed.

Phosphates for use in the present invention include phosphates, acidphosphates, phosphites and acid phosphites. The phosphates includetriaryl phosphates, trialkyl phosphates, trialkylaryl phosphates,triarylalkyl phosphates and trialkenyl phosphates. As specific examplesof these, referred to are triphenyl phosphate, tricresyl phosphate,benzyldiphenyl phosphate, ethyldiphenyl phosphate, tributyl phosphate,ethyldibutyl phosphate, cresyldiphenyl phosphate, dicresylphenylphosphate, ethylphenyldiphenyl phosphate, diethylphenylphenyl phosphate,propylphenyldiphenyl phosphate, dipropylphenylphenyl phosphate,triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyldiphenylphosphate, dibutylphenylphenyl phosphate, tributylphenyl phosphate,trihexyl phosphate, tri(2-ethylhexyl) phosphate, tridecyl phosphate,trilauryl phosphate, trimyristyl phosphate, tripalmityl phosphate,tristearyl phosphate, and trioleyl phosphate. The acid phosphatesinclude, for example, 2-ethylhexyl acid phosphate, ethyl acid phosphate,butyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate,isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate,stearyl acid phosphate, and isostearyl acid phosphate.

The phosphites include, for example, triethyl phosphite, tributylphosphite, triphenyl phosphite, tricresyl phosphite, tri(nonylphenyl)phosphite, tri(2-ethylhexyl) phosphite, tridecyl phosphite, trilaurylphosphite, triisooctyl phosphite, diphenylisodecyl phosphite, tristearylphosphite, and trioleyl phosphite.

The acid phosphites include, for example, dibutyl hydrogenphosphite,dilauryl hydrogenphosphite, dioleyl hydrogenphosphite, distearylhydrogenphosphite, and diphenyl hydrogenphosphite.

Amines that form amine salts with such phosphates include, for example,mono-substituted amines, di-substituted amines and tri-substitutedamines. Examples of the mono-substituted amines include butylamine,pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine,stearylamine, oleylamine and benzylamine; and those of thedi-substituted amines include dibutylamine, dipentylamine, dihexylamine,dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine,dioleylamine, dibenzylamine, stearyl monoethanolamine, decylmonoethanolamine, hexyl monopropanolamine, benzyl monoethanolamine,phenyl monoethanolamine, and tolyl monopropanolamine. Examples oftri-substituted amines include tributylamine, tripentylamine,trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine,tristearylamine, trioleylamine, tribenzylamine, dioleylmonoethanolamine, dilauryl monopropanolamine, dioctyl monoethanolamine,dihexyl monopropanolamine, dibutyl monopropanolamine, oleyldiethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyldipropanolamine, butyl diethanolamine, benzyl diethanolamine, phenyldiethanolamine, tolyl dipropanolamine, xylyl diethanolamine,triethanolamine, and tripropanolamine. Phosphates or their amine saltsare added to the base oil in an amount of from 0.03 to 5% by weight,preferably from 0.1 to 4% by weight, relative to the total weight of thecomposition.

Carboxylic acids to be reacted with amines include, for example,aliphatic carboxylic acids, dicarboxylic acids (dibasic acids), andaromatic carboxylic acids. The aliphatic carboxylic acids have from 8 to30 carbon atoms, and may be saturated or unsaturated, and linear orbranched. Specific examples of the aliphatic carboxylic acids includepelargonic acid, lauric acid, tridecanoic acid, myristic acid, palmiticacid, stearic acid, isostearic acid, eicosanoic acid, behenic acid,triacontanoic acid, caproleic acid, undecylenic acid, oleic acid,linolenic acid, erucic acid, and linoleic acid. Specific examples of thedicarboxylic acids include octadecylsuccinic acid, octadecenylsuccinicacid, adipic acid, azelaic acid, and sebacic acid. One example of thearomatic carboxylic acids is salicylic acid. The amines to be reactedwith carboxylic acids include, for example, polyalkylene-polyamines suchas diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine,dipropylenetriamine, tetrapropylenepentamine, and hexabutyleneheptamine;and alkanolamines such as monoethanolamine and diethanolamine. Of these,preferred are a combination of isostearic acid andtetraethylenepentamine, and a combination of oleic acid anddiethanolamine. The reaction products of carboxylic acids and amines areadded to the base oil in an amount of from 0.01 to 5% by weight,preferably from 0.03 to 3% by weight, relative to the total weight ofthe composition.

Important components are phosphites, thiophosphites phosphates, andthiophosphates, including mixed materials having, for instance, one ortwo sulfur atoms, i.e., monothio- or dithio compounds. As used herein,the term “hydrocarbyl substituent” or “hydrocarbyl group” is used in itsordinary sense, which is well-known to those skilled in the art.Specifically, it refers to a group having a carbon atom directlyattached to the remainder of the molecule and having predominantlyhydrocarbon character. Examples of hydrocarbyl groups include:

Hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl),alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-,aliphatic-, and alicyclic-substituted aromatic substituents, as well ascyclic substituents wherein the ring is completed through anotherportion of the molecule (e.g., two substituents together form analicyclic radical); the substituted hydrocarbon substituents, that is,substituents containing non-hydrocarbon groups which, in the context ofthis invention, do not alter the predominantly hydrocarbon substituent(e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto,alkylmercapto, nitro, nitroso, and sulfoxy); and hetero-atom containingsubstituents, that is, substituents which, while having a predominantlyhydrocarbon character, in the context of this invention, contain otherthan carbon in a ring or chain otherwise composed of carbon atoms.Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituentsas pyridyl, furyl, thienyl and imidazolyl. In general, no more than two,preferably no more than one, non-hydrocarbon substituent will be presentfor every ten carbon atoms in the hydrocarbyl group; typically, therewill be no non-hydrocarbon substituents in the hydrocarbyl group.

The term “hydrocarbyl group,” in the context of the present invention,is also intended to encompass cyclic hydrocarbyl or hydrocarbylenegroups, where two or more of the alkyl groups in the above structurestogether form a cyclic structure. The hydrocarbyl or hydrocarbylenegroups of the present invention generally are alkyl or cycloalkyl groupswhich contain at least 3 carbon atoms. Preferably or optimallycontaining sulfur, nitrogen, or oxygen, they will contain 4 to 24, andalternatively 5 to 18 carbon atoms. In another embodiment they containabout 6, or exactly 6 carbon atoms. The hydrocarbyl groups can betertiary or preferably primary or secondary groups; in one embodimentthe component is a di(hydrocarbyl)hydrogen phosphite and each of thehydrocarbyl groups is a primary alkyl group; in another embodiment thecomponent is a di(hydrocarbyl)hydrogen phosphite and each of thehydrocarbyl groups is a secondary alkyl group. In yet another embodimentthe component is a hydrocarbylenehydrogen phosphite.

Examples of straight chain hydrocarbyl groups include methyl, ethyl,n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl,stearyl, n-hexadecyl, n-octadecyl, oleyl, and cetyl. Examples ofbranched-chain hydrocarbon groups include isopropyl, isobutyl, secondarybutyl, tertiary butyl, neopentyl, 2-ethylhexyl, and 2,6-dimethylheptyl.Examples of cyclic groups include cyclobutyl, cyclopentyl,methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, andcyclooctyl. A few examples of aromatic hydrocarbyl groups and mixedaromatic-aliphatic hydrocarbyl groups include phenyl, methylphenyl,tolyl, and naphthyl.

The R groups can also comprise a mixture of hydrocarbyl groups derivedfrom commercial alcohols. Examples of some monohydric alcohols andalcohol mixtures include the commercially available “Alfol™” alcoholsmarketed by Continental Oil Corporation. Alfol™ 810, for instance, is amixture containing alcohols consisting essentially of straight chain,primary alcohols having from 8 to 12 carbon atoms. Alfol™ 12 is amixture of mostly C12 fatty alcohols; Alfol™ 22+ comprises C 18-28primary alcohols having mostly C 22 alcohols, and so on. Variousmixtures of monohydric fatty alcohols derived from naturally occurringtriglycerides and ranging in chain length from C 8 to C 18 are availablefrom Procter & Gamble Company. “Neodol™” alcohols are available fromShell Chemical Co., where, for instance, Neodol™ 25 is a mixture of C 12to C 15 alcohols.

Specific examples of some of the phosphites and thiophosphites withinthe scope of the invention include phosphorous acid, mono-, di-, ortri-thiophosphorous acid, mono-, di-, or tri-propyl phosphite or mono-,di-, or tri-thiophosphite; mono-, di-, or tri-butyl phosphite or mono-,di-, or tri-thiophosphite; mono-, di-, or tri-amyl phosphite or mono-,di-, or tri-thiophosphite; mono-, di-, or tri-hexyl phosphite or mono-,di-, or tri-thiophosphite; mono-, di-, or tri-phenyl phosphite or mono-,di-, or tri-thiophosphite; mono-, di-, or tri-tolyl phosphite or mono-,di-, or tri-thiophosphite; mono-, di-, or tri-cresyl phosphite or mono-,di-, or tri-thiophosphite; dibutyl phenyl phosphite or mono-, di-, ortri-phosphite, amyl dicresyl phosphite or mono-, di-, ortri-thiophosphite, and any of the above with substituted groups, such aschlorophenyl or chlorobutyl.

Specific examples of the phosphates and thiophosphates within the scopeof the invention include phosphoric acid, mono-, di-, ortri-thiophosphoric acid, mono-, di-, or tri-propyl phosphate or mono-,di-, or tri-thiophosphate; mono-, di-, or tri-butyl phosphate or mono-,di-, or tri-thiophosphate; mono-, di-, or tri-amyl phosphate or mono-,di-, or tri-thiophosphate; mono-, di-, or tri-hexyl phosphate or mono-,di-, or tri-thiophosphate; mono-, di-, or tri-phenyl phosphate or mono-,di-, or tri-thiophosphate; mono-, di-, or tritolyl phosphate or mono-,di-, or trithiophosphate; mono-, di-, or tri-cresyl phosphate or mono-,di-, or tri-thiophosphate; dibutyl phenyl phosphate or mono-, di-, ortri-phosphate, amyl dicresyl phosphate or mono-, di-, ortri-thiophosphate, and any of the above with substituted groups, such aschlorophenyl or chlorobutyl.

The phosphorus compounds of the present invention are prepared by wellknown reactions. One route the reaction of an alcohol or a phenol withphosphorus trichloride or by a transesterification reaction. Alcoholsand phenols can be reacted with phosphorus pentoxide to provide amixture of an alkyl or aryl phosphoric acid and a dialkyl or diarylphosphoric acid. Alkyl phosphates can also be prepared by the oxidationof the corresponding phosphites. Thiophosphates can be prepared by thereaction of phosphites with elemental sulfur. In any case, the reactioncan be conducted with moderate heating. Moreover, various phosphorusesters can be prepared by reaction using other phosphorus esters asstarting materials. Thus, medium chain (C9 to C22) phosphorus estershave been prepared by reaction of dimethylphosphite with a mixture ofmedium-chain alcohols by means of a thermal transesterification or anacid- or base-catalyzed transesterification; see for example U.S. Pat.No. 4,652,416. Most such materials are also commercially available; forinstance, triphenyl phosphite is available from Albright and Wilson asDuraphos TPP™; di-n-butyl hydrogen phosphite from Albright and Wilson asDuraphos DBHP™; and triphenylthiophosphate from Ciba Specialty Chemicalsas Irgalube TPPT™.

The other major component of the present composition is a hydrocarbonhaving ethylenic unsaturation. This would normally be described as anolefin or a diene, triene, polyene, and so on, depending on the numberof ethylenic unsaturations present. Preferably the olefin is monounsaturated, that is, containing only a single ethylenic double bond permolecule. The olefin can be a cyclic or a linear olefin. If a linearolefin, it can be an internal olefin or an alpha-olefin. The olefin canalso contain aromatic unsaturation, i.e., one or more aromatic rings,provided that it also contains ethylenic (non-aromatic) unsaturation.

The olefin normally will contain 6 to 30 carbon atoms. Olefins havingsignificantly fewer than 6 carbon atoms tend to be volatile liquids orgases which are not normally suitable for formulation into a compositionsuitable as an antiwear lubricant. Preferably the olefin will contain 6to 18 or 6 to 12 carbon atoms, and alternatively 6 or 8 carbon atoms.

Among suitable olefins are alkyl-substituted cyclopentenes, hexenes,cyclohexene, alkyl-substituted cyclohexenes, heptenes, cycloheptenes,alkyl-substituted cycloheptenes, octenes including diisobutylene,cyclooctenes, alkyl-substituted cyclooctenes, nonenes, decenes,undecenes, dodecenes including propylene tetramer, tridecenes,tetradecenes, pentadecenes, hexadecenes, heptadecenes, octadecenes,cyclooctadiene, norbornene, dicyclopentadiene, squalene,diphenylacetylene, and styrene. Highly preferred olefins are cyclohexeneand 1-octene.

Examples of esters of the dialkylphosphorodithioic acids include estersobtained by reaction of the dialkyl phosphorodithioic acid with analpha, beta-unsaturated carboxylic acid (e.g., methyl acrylate) and,optionally an alkylene oxide such as propylene oxide.

Generally, the compositions of the present invention will containvarying amounts of one or more of the above-identified metaldithiophosphates such as from about 0.01 to about 2% by weight, and moregenerally from about 0.01 to about 1% by weight, based on the weight ofthe total composition.

The hydrocarbyl in the dithiophosphate may be alkyl, cycloalkyl, aralkylor alkaryl groups, or a substantially hydrocarbon group of similarstructure. Illustrative alkyl groups include isopropyl, isobutyl,n-butyl, sec-butyl, the various amyl groups, n-hexyl, methylisobutyl,heptyl, 2-ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl, decyl,dodecyl, tridecyl, etc. Illustrative lower alkylphenyl groups includebutylphenyl, amylphenyl, heptylphenyl, etc. Cycloalkyl groups likewiseare useful and these include chiefly cyclohexyl and the loweralkyl-cyclohexyl radicals. Many substituted hydrocarbon groups may alsobe used, e.g., chloropentyl, dichlorophenyl, and dichlorodecyl.

The phosphorodithioic acids from which the metal salts useful in thisinvention are prepared are well known. Examples ofdihydrocarbylphosphorodithioic acids and metal salts, and processes forpreparing such acids and salts are found in, for example U.S. Pat. Nos.4,263,150; 4,289,635; 4,308,154; and 4,417,990. These patents are herebyincorporated by reference.

The phosphorodithioic acids are prepared by the reaction of a phosphorussulfide with an alcohol or phenol or mixtures of alcohols. A typicalreaction involves four moles of the alcohol or phenol and one mole ofphosphorus pentasulfide, and may be carried out within the temperaturerange from about 50C. to about 200C. Thus, the preparation ofO,O-di-n-hexyl phosphorodithioic acid involves the reaction of a mole ofphosphorus pentasulfide with four moles of n-hexyl alcohol at about 100Cfor about two hours. Hydrogen sulfide is liberated and the residue isthe desired acid. The preparation of the metal salts of these acids maybe effected by reaction with metal compounds as well known in the art.

The metal salts of dihydrocarbyldithiophosphates which are useful inthis invention include those salts containing Group I metals, Group IImetals, aluminum, lead, tin, molybdenum, manganese, cobalt, and nickel.The Group II metals, aluminum, tin, iron, cobalt, lead, molybdenum,manganese, nickel and copper are among the preferred metals. Zinc andcopper are especially useful metals. Examples of metal compounds whichmay be reacted with the acid include lithium oxide, lithium hydroxide,sodium hydroxide, sodium carbonate, potassium hydroxide, potassiumcarbonate, silver oxide, magnesium oxide, magnesium hydroxide, calciumoxide, zinc hydroxide, strontium hydroxide, cadmium oxide, cadmiumhydroxide, barium oxide, aluminum oxide, iron carbonate, copperhydroxide, lead hydroxide, tin butylate, cobalt hydroxide, nickelhydroxide, nickel carbonate, and the like.

In some instances, the incorporation of certain ingredients such assmall amounts of the metal acetate or acetic acid in conjunction withthe metal reactant will facilitate the reaction and result in animproved product. For example, the use of up to about 5% of zinc acetatein combination with the required amount of zinc oxide facilitates theformation of a zinc phosphorodithioate with potentially improvedperformance properties.

Especially useful metal phosphorodithloates can be prepared fromphosphorodithloic acids which in turn are prepared by the reaction ofphosphorus pentasulfide with mixtures of alcohols. In addition, the useof such mixtures enables the utilization of less expensive alcoholswhich individually may not yield oil-soluble phosphorodithioic acids.Thus a mixture of isopropyl and hexylalcohols can be used to produce avery effective, oil-soluble metal phosphorodithioate. For the samereason mixtures of phosphorodithioic acids can be reacted with the metalcompounds to form less expensive, oil-soluble salts.

The mixtures of alcohols may be mixtures of different primary alcohols,mixtures of different secondary alcohols or mixtures of primary andsecondary alcohols. Examples of useful mixtures include: n-butanol andn-octanol; n-pentanol and 2-ethyl-1-hexanol; isobutanol and n-hexanol;isobutanol and isoamyl alcohol; isopropanol and 2-methyl-4-pentanol;isopropanol and sec-butyl alcohol; isopropanol and isooctyl alcohol; andthe like.

Organic triesters of phosphorus acids are also employed in lubricants.Typical esters include triarylphosphates, trialkyl phosphates, neutralalkylaryl phosphates, alkoxyalkyl phosphates, triaryl phosphite,trialkylphosphite, neutral alkyl aryl phosphites, neutral phosphonateesters and neutral phosphine oxide esters. In one embodiment, the longchain dialkyl phosphonate esters are used. More preferentially, thedimethyl-, diethyl-, and dipropyl-oleyl phosphonates can be used.Neutral acids of phosphorus acids are the triesters rather than an acid(HO—P) or a salt of an acid.

Any C4 to C8 alkyl or higher phosphate ester may be employed in theinvention. For example, tributyl phosphate (TBP) and tri isooctalphosphate (TOF) can be used. The specific triphosphate ester orcombination of esters can easily be selected by one skilled in the artto adjust the density, viscosity etc. of the formulated fluid. Mixedesters, such as dibutyl octyl phosphate or the like may be employedrather than a mixture of two or more trialkyl phosphates.

A trialkyl phosphate is often useful to adjust the specific gravity ofthe formulation, but it is desirable that the specific trialkylphosphate be a liquid at low temperatures. Consequently, a mixed estercontaining at least one partially alkylated with a C3 to C4 alkyl groupis very desirable, for example, 4-isopropylphenyl diphenyl phosphate or3-butylphenyl diphenyl phosphate. Even more desirable is a triarylphosphate produced by partially alkylating phenol with butylene orpropylene to form a mixed phenol which is then reacted with phosphorusoxychloride as taught in U.S. Pat. No. 3,576,923.

Any mixed triaryl phosphate (TAP) esters may be used as cresyl diphenylphosphate, tricresyl phosphate, mixed xylyl cresyl phosphates, loweralkylphenyl/phenyl phosphates, such as mixed isopropylphenyl/phenylphosphates, t-butylphenyl phenyl phosphates. These esters are usedextensively as plasticizers, functional fluids, gasoline additives,flame-retardant additives and the like.

An Extreme pressure agent, sulfur-based extreme pressure agents, such assulfides, sulfoxides, sulfones, thiophosphinates, thiocarbonates,sulfurized fats and oils, sulfurized olefins and the like;phosphorus-based extreme pressure agents, such as phosphoric acid esters(e.g., tricresyl phosphate (TCP) and the like), phosphorous acid esters,phosphoric acid ester amine salts, phosphorous acid ester amine salts,and the like; halogen-based extreme pressure agents, such as chlorinatedhydrocarbons and the like; organometallic extreme pressure agents, suchas thiophosphoric acid salts (e.g., zinc dithiophosphate (ZnDTP) and thelike) and thiocarbamic acid salts; and the like can be used. As theanti-wear agent, organomolybdenum compounds such as molybdenumdithiophosphate (MoDTP), molybdenum dithiocarbamate (MODTC) and thelike; organoboric compounds such as alkylmercaptyl borate and the like;solid lubricant anti-wear agents such as graphite, molybdenum disulfide,antimony sulfide, boron compounds, polytetrafluoroethylene and the like;and the like can be used.

The phosphoric acid ester, thiophosphoric acid ester, and amine saltthereof functions to enhance the lubricating performances, and can beselected from known compounds conventionally employed as extremepressure agents. Generally employed are phosphoric acid esters, athiophosphoric acid ester, or an amine salt thereof which has an alkylgroup, an alkenyl group, an alkylaryl group, or an aralkyl group, any ofwhich contains approximately 3 to 30 carbon atoms.

Examples of the phosphoric acid esters include aliphatic phosphoric acidesters such as triisopropyl phosphate, tributyl phosphate, ethyl dibutylphosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, trilaurylphosphate, tristearyl phosphate, and trioleyl phosphate; and aromaticphosphoric acid esters such as benzyl phenyl phosphate, allyl diphenylphosphate, triphenyl phosphate, tricresyl phosphate, ethyl diphenylphosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate,ethylphenyl diphenyl phosphate, diethylphenyl phenyl phosphate,propylphenyl diphenyl phosphate, dipropylphenyl phenyl phosphate,triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyldiphenyl phosphate, dibutylphenyl phenyl phosphate, and tributylphenylphosphate. Preferably, the phosphoric acid ester is a trialkylphenylphosphate.

Examples of the thiophosphoric acid esters include aliphaticthiophosphoric acid esters such as triisopropyl thiophosphate, tributylthiophosphate, ethyl dibutyl thiophosphate, trihexyl thiophosphate,tri-2-ethylhexyl thiophosphate, trilauryl thiophosphate, tristearylthiophosphate, and trioleyl thiophosphate; and aromatic thiophosphoricacid esters such as benzyl phenyl thiophosphate, allyl diphenylthiophosphate, triphenyl thiophosphate, tricresyl thiophosphate, ethyldiphenyl thiophosphate, cresyl diphenyl thiophosphate, dicresyl phenylthiophosphate, ethylphenyl diphenyl thiophosphate, diethylphenyl phenylthiophosphate, propylphenyl diphenyl thiophosphate, dipropylphenylphenyl thiophosphate, triethylphenyl thiophosphate, tripropylphenylthiophosphate, butylphenyl diphenyl thiophosphate, dibutylphenyl phenylthiophosphate, and tributylphenyl thiophosphate. Preferably, thethiophosphoric acid ester is a trialkylphenyl thiophosphate.

Also employable are amine salts of the above-mentioned phosphates andthiophosphates. Amine salts of acidic alkyl or aryl esters of thephosphoric acid and thiophosphoric acid are also employable. Preferably,the amine salt is an amine salt of trialkylphenyl phosphate or an aminesalt of alkyl phosphate.

One or any combination of the compounds selected from the groupconsisting of a phosphoric acid ester, a thiophosphoric acid ester, andan amine salt thereof may be used.

The phosphorus acid ester and/or its amine salt function to enhance thelubricating performances, and can be selected from known compoundsconventionally employed as extreme pressure agents. Generally employedare a phosphorus acid ester or an amine salt thereof which has an alkylgroup, an alkenyl group, an alkylaryl group, or an aralkyl group, any ofwhich contains approximately 3 to 30 carbon atoms.

Examples of the phosphorus acid esters include aliphatic phosphorus acidesters such as triisopropyl phosphite, tributyl phosphite, ethyl dibutylphosphite, trihexyl phosphite, tri-2-ethylhexylphosphite, trilaurylphosphite, tristearyl phosphite, and trioleyl phosphite; and aromaticphosphorus acid esters such as benzyl phenyl phosphite, allyldiphenylphosphite, triphenyl phosphite, tricresyl phosphite, ethyldiphenyl phosphite, tributyl phosphite, ethyl dibutyl phosphite, cresyldiphenyl phosphite, dicresyl phenyl phosphite, ethylphenyl diphenylphosphite, diethylphenyl phenyl phosphite, propylphenyl diphenylphosphite, dipropylphenyl phenyl phosphite, triethylphenyl phosphite,tripropylphenyl phosphite, butylphenyl diphenyl phosphite, dibutylphenylphenyl phosphite, and tributylphenyl phosphite. Also favorably employedare dilauryl phosphite, dioleyl phosphite, dialkyl phosphites, anddiphenyl phosphite. Preferably, the phosphorus acid ester is a dialkylphosphite or a trialkyl phosphite.

The phosphate salt may be derived from a polyamine. The polyaminesinclude alkoxylated diamines, fatty polyamine diamines,alkylenepolyamines, hydroxy containing polyamines, condensed polyaminesarylpolyamines, and heterocyclic polyamines. Commercially availableexamples of alkoxylated diamines include those amine where y in theabove formula is one. Examples of these amines include Ethoduomeen T/13and T/20 which are ethylene oxide condensation products ofN-tallowtrimethylenediamine containing 3 and 10 moles of ethylene oxideper mole of diamine, respectively.

In another embodiment, the polyamine is a fatty diamine. The fattydiamines include mono- or dialkyl, symmetrical or asymmetrical ethylenediamines, propane diamines (1,2, or 1,3), and polyamine analogs of theabove. Suitable commercial fatty polyamines are Duomeen C.(N-coco-1,3-diaminopropane), Duomeen S(N-soya-1,3-diaminopropane),Duomeen T (N-tallow-1,3-diaminopropane), and Duomeen 0(N-oleyl-1,3-diaminopropane). “Duomeens” are commercially available fromArmak Chemical Co., Chicago, Ill.

Such alkylenepolyamines include methylenepolyamines, ethylenepolyamines,butylenepolyamines, propylenepolyamines, pentylenepolyamines, etc. Thehigher homologs and related heterocyclic amines such as piperazines andN-amino alkyl-substituted piperazines are also included. Specificexamples of such polyamines are ethylenediamine, triethylenetetramine,tris-(2-aminoethyl)amine, propylenediamine, trimethylenediamine,tripropylenetetramine, tetraethylenepentamine, hexaethyleneheptamine,pentaethylenehexamine, etc. Higher homologs obtained by condensing twoor more of the above-noted alkyleneamines are similarly useful as aremixtures of two or more of the aforedescribed polyamines.

In one embodiment the polyamine is an ethylenepolyamine. Such polyaminesare described in detail under the heading Ethylene Amines in KirkOthmer's “Encyclopedia of Chemical Technology”, 2d Edition, Vol. 7,pages 22-37, Interscience Publishers, New York (1965).Ethylenepolyamines are often a complex mixture of polyalkylenepolyaminesincluding cyclic condensation products.

Other useful types of polyamine mixtures are those resulting fromstripping of the above-described polyamine mixtures to leave, asresidue, what is often termed “polyamine bottoms”. In general,alkylenepolyamine bottoms can be characterized as having less than 2%,usually less than 1% (by weight) material boiling below about 200C. Atypical sample of such ethylene polyamine bottoms obtained from the DowChemical Company of Freeport, Tex. designated “E-100”. Thesealkylenepolyamine bottoms include cyclic condensation products such aspiperazine and higher analogs of diethylenetriamine,triethylenetetramine and the like. These alkylenepolyamine bottoms canbe reacted solely with the acylating agent or they can be used withother amines, polyamines, or mixtures thereof. Another useful polyamineis a condensation reaction between at least one hydroxy compound with atleast one polyamine reactant containing at least one primary orsecondary amino group. The hydroxy compounds are preferably polyhydricalcohols and amines. The polyhydric alcohols are described below. (Seecarboxylic ester dispersants.) In one embodiment, the hydroxy compoundsare polyhydric amines. Polyhydric amines include any of theabove-described monoamines reacted with an alkylene oxide (e.g.,ethylene oxide, propylene oxide, butylene oxide, etc.) having from twoto about 20 carbon atoms, or from two to about four. Examples ofpolyhydric amines include tri-(hydroxypropyl)amine,tris-(hydroxymethyl)amino methane, 2-amino-2-methyl-1,3-propanediol,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, andN,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine, preferablytris(hydroxymethyl)aminomethane (THAM).

Polyamines which react with the polyhydric alcohol or amine to form thecondensation products or condensed amines, are described above.Preferred polyamines include triethylenetetramine (TETA),tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), andmixtures of polyamines such as the above-described “amine bottoms”.

Examples of extreme pressure additives include sulphur-based extremepressure additives such as dialkyl sulphides, dibenzyl sulphide, dialkylpolysulphides, dibenzyl disulphide, alkyl mercaptans, dibenzothiopheneand 2,2′-dithiobis(benzothiazole); phosphorus-based extreme pressureadditives such as trialkyl phosphates, triaryl phosphates, trialkylphosphonates, trialkyl phosphites, triaryl phosphites anddialkylhydrozine phosphites, and phosphorus- and sulphur-based extremepressure additives such as zinc dialkyldithiophosphates,dialkylthiophosphoric acid, trialkyl thiophosphate esters, acidicthiophosphate esters and trialkyl trithiophosphates. These extremepressure additives can be used individually or in the form of mixtures,conveniently in an amount within the range from 0.1 to 2 parts byweight, per 100 parts by weight of the base oil.

All the above can be performance enhanced using a variety of cobasestocks, AN, AB, ADPO, ADPS, ADPM, and/or a variety of mono-basic,di-basic, and tribasic esters in conjunction with low sulfur, lowaromatic, low iodine number, low bromine number, high analine point,isoparafin.

EXAMPLES

We formulated three inventive gear oil blends for comparison against twocommercially available gear oils. All the inventive blends contained twobase stocks and contained the same standard gear oil additive package.

The first blend comprises a metallocene catalyzed PAO base stock with aviscosity of 620 cSt, Kv100° C. The second base stock contained a PAOwith a viscosity of 4 cSt, Kv1° C. The blend also includes alkylatednapthalene, phalate ester and adipate ester along with a gear oiladditive pack.

The second blend comprises a metallocene catalyzed PAO base stock with aviscosity of 620 cSt, Kv100° C. The second PAO base stock with aviscosity of 4 cSt, Kv100° C. The blend also includes adipate esteralong with a gear oil additive pack.

The third blend comprises a regular high viscosity PAO with a viscosityof 100 cSt, Kv100° C. and a low viscosity PAO with a viscosity of 6 cSt,Kv100° C. The blend also includes alkylated napthalene, phalate esterand adipate ester along with a gear oil additive pack.

Table 4 shows the formulations of the three novel blends relative to thetwo commercial synthetic products which serve as the benchmarks ofperformance as shown in table 4 the benefit is most pronounced in thewhen compared to synethic gear oil A which is a traditional PAO gear oilwith some alkylated naphtaleline. The three novel formulations providecomparable MSWG efficiency and operating temperature performance toPolyalkylene glycols (“PAGs”) oils but retain the benefits of PAO oils.

PAGs have some excellent properties but also have some inherent poorproperties. The excellent properties of PAGS include viscosity index,foam and air control, efficiency and oxidative stability. The poorproperties include water tolerance, rust control and compatibility. Thenovel formulations in Table 4 provide all around excellent propertiesincluding comparable performance to PAGs for excellent viscosity index,foam and air control, efficiency and oxidative stability while alsoproviding good water tolerance, compatibility and rust control. TABLE 4ISO VG 460 EXPERIMENTAL COMMERCIAL Kv100° C. = A B C D E ConventionalPAG-based 50-60 cSt PAO-based lubricant mPAO 620 cSt 45.7 51.7 19.7lubricant mPAO 450 cSt 54.7 mPAO 300 cSt 60.7 40 cSt PAO 70 4 cSt PAO 4138 35 29 Cobase stock and 13.3 10.3 10.3 13.3 13.3 Additive package WormGear Ave 152 157 159 169 168 175 150 Sump Temp ° F. Worm Gear Av. 81.179.9 79.3 77.6 77.8 76.7 80.5 Efficiency ASTM D3427 75° C. 5.2 5.7 5.95.4 7.1 22.4 21 Time to 0.2% Air (min) ASTM D97 Pour −42 −42 −39 −48 −39−42 −33 Point ° C.

The data from table 4 is shown in FIG. 3. FIG. 3 is a graph illustratingthe improved air release benefits profile of A, B, C, D, and E of highviscosity metallocene catalyzed base stocks in bi-modal blend ascompared to the profile of a high viscosity PAO base stock in a blendwith a low viscosity base stock. And a PAG based lubricant.

While the examples have been to gear oils, these examples are notintended to be limiting. The novel formulations provides improvedproperties of all lubricating uses including but not limited toindustrial, engine and hydraulic oils.

The operating temperatures data from table 4 is shown in FIG. 4. FIG. 4shows the of the three experimental extreme-modal formulations A, B, C,D, and E relative to the current commercially available synthetic PAOand PAG gear oils. Indeed, the thermal performance of these experimentalformulations rival that of the commercially available PAGs.

The metallocene based bases stocks in a bi-modal formula further providefavorable air release benefits. FIG. 5 illustrates the improved airrelease of the novel formulations in Table 4 when compare tocommercially available gear oils including typical PAO and PAG blends.

In addition, the metallocene based bases stocks in a bi-modal formulaprovides favorable low temperature benefits including favorable pourpoints compared to PAGs. Favorable pour points permit better oilpumpability and better equipment startup at low temperatures. For pourpoint testing, ASTM D97 is most often utilized. In this method, oil isslowly cooled at a specific rate, and examined at 3° C. intervals forflow characteristics. The lowest temperature where movement is observedis the pour point. FIG. 6 illustrates the improved pour points of thenovel formulations in Table 4 when compared to commercially availablePAG gear oil blends as well as equivalent performance when compared totypical PAO gear oil blends.

In addition to the above examples, there are other base stocks that givefavorable performance when combined with high viscosity metallocenecatalyzed base stocks of greater than 300 cSt, Kv100° C. These basestocks include but are not limited to GTL, Group III., Group II, PIB,Group V base stocks, including alkylnaphthalenes, alkylbenzenes,polyalkylene glycols and esters including polyol esters, trimelliticesters, aromatic esters, dibasic esters and monobasic esters. In all theabove cases, some portion of Group I base stock can be added to achievesuitable viscosity and to impart solvency/dispersancy and other propertytypical to Group I base stocks.

In addition, based on the disclosure herein other base stocks of widelydisparate viscosities that give a “bi-modal” or “extreme-modal” blendingresult can also be envisioned with the benefit of the disclosure hereinto deliver favorable lubricating properties. These properties includebut are not limited to micropitting, air release, pour point, lowtemperature viscosity, pour point, shear stability, and any combinationthereof. While the benefits discussed herein are primarily for the useof gear oil, the benefits would apply to all lubricants includingmarine, automotive, and industrial. The claims are intended to includeall suitable lubricant applications.

In one embodiment, no VI improvers are needed due to the high inherentVI of the base stocks. This benefit permits the ability to avoid VIimprovers that may adversely affect shear stability. In this embodiment,the shear stability of the lubricant should be less than 15 percent andeven more preferably less than 10 percent and in the most preferredembodiment, there will be essentially no VI improvers.

In a preferred embodiment, no transition or alkali metals are used inthe finished formulation. This finished formulation would provideenhanced hydrolytic stability.

In another embodiment, another benefit of the improved base stocksproperties is the ability to use less additives. In a preferredembodiment, the base stock combination provides the ability to use treatrates less than 10 percent and less than 5 percent.

1. A lubricating oil, comprising a) at least two base stocks; b) a firstbase having a viscosity at least 300 cSt, Kv100° C. and the first basestock having a molecular weight distribution (MWD) as a function ofviscosity at least 10 percent less than algorithmMWD=0.2223+1.0232*log(Kv at 100° C. in cSt); c) a second base stock witha viscosity less than 100 cSt, Kv100° C.
 2. The lubricating oil of claim1 wherein the viscosity difference between the first and the second basestocks is greater than 250 cSt, Kv100° C.
 3. The lubricating oil ofclaim 1 wherein the first base stock is a metallocene catalyzed PAO basestock.
 4. The lubricating oil of claim 1 wherein the second base stockis chosen from the group consisting of GTL base stock, wax derived basestock, Poly-Alpha-Olefin (PAO), Brightstocks, Brightstocks with PIB,Group I base stocks, Group II base stocks, Group III base stocks, GroupV base stocks, Group VI base stocks, and any combination thereof.
 5. Thelubricating oil of claim 1 further comprising at least one additive, theadditive chosen from the group consisting of antiwear, antioxidant,defoamant, demulsifier, detergent, dispersant, metal passivator,friction reducer, rust inhibitor, and any combination thereof.
 6. Thelubricating oil of claim 1 further comprising a third base stock.
 7. Thelubricating oil of claim 6, wherein the third base stock is chosen froma group consisting of a PAO with a viscosity of at least 1.5 cSt, Kv100°C. and no more than 100 cSt, Kv100° C., a Group V base stock includingester base stock, alkylated aromatic and any combination thereof.
 8. Thelubricating oil of claim 6 wherein the first base stock has a viscositygreater than 400 cSt, Kv100° C.
 9. The lubricating oil of claim 7wherein the third base stock, is an alkylated naphthalene or alkylatedbenzene base stocks.
 10. The lubricating oil of claim 1 wherein thesecond base stock has a viscosity greater than 1.5 and less than 60 cSt,Kv100° C.
 11. The lubricating oil of claim 1 wherein the viscositydifference between the first base stock and the second base stock isgreater than 400 cSt, Kv100° C.
 12. The lubricating oil of claim 1wherein the first base stock has a molecular weight distribution lessthan algorithm:MWD=0.41667+0.725*log(Kv at 100° C. in cSt).
 13. A lubricating oil,comprising a) at least two base stocks; b) a first base stock comprisinga metallocene catalyzed PAO with a viscosity greater than 300 cSt,Kv100° C.; c) a second base stock comprising a oil with a viscosity lessthan 100 cSt, Kv100° C.
 14. The lubricating oil of claim 13 wherein thefirst base stock is greater than 250 cSt, Kv100° C.
 15. The lubricatingoil of claim 13 wherein the first base stock has a molecular weightdistribution (MWD) as a function of viscosity at least 10 percent lessthan algorithmMWD=0.2223+1.0232*log(Kv at 100° C. in cSt).
 16. The lubricating oil ofclaim 13 wherein the second base stock has a viscosity greater than 1.5cSt, Kv100° C.
 17. The lubricating oil of claim 13 further comprising analkylated naphthalene and an additive package.
 18. The lubricating oilof claim 13 wherein the first base stock has a molecular weightdistribution less than algorithm:MWD=0.41667+0.725*log(Kv at 100° C. in cSt).
 19. The lubricating oil ofclaim 13 wherein the second base stock is is chosen from the groupconsisting of GTL lubricants, wax derived lubricants, Poly Alpha Olefin,Brightstocks, Brightstocks with PIB, Group I base stocks, Group II basestocks, Group III base stocks, Group V and any combination thereof. 20.The lubricating oil of claim 13 further comprising an additive, theadditive chosen from the group consisting of antiwear, antioxidant,defoamant, demulsifier, detergent, dispersant, metal passivator,friction reducer, rust inhibitor, and any combination thereof.
 21. Thelubricating oil of claim 13 further comprising at least one additivechosen to obtain favorable lubricant properties from the groupconsisting of micropitting, air release, pour point, low temperatureviscosity, pour point, shear stability, lower oil operating temperature,energy efficiency and any combination thereof.
 22. The lubricating oilof claim 13 wherein the viscosity difference between the first basestock and the second base stock is greater than 300 cSt, Kv100° C. 23.The lubricating oil of claim 13 wherein the viscosity difference betweenthe first base stock and the second base stock is greater than 400 cSt,Kv100° C.
 24. A method of blending a lubricating oil, comprising, a)obtaining a first synthetic base stock lubricant the first base stockhaving a viscosity greater than 300 cSt, Kv100° C. and the first basesstock having a molecular weight distribution (MWD) as a function ofviscosity at least 10 percent less than algorithmMWD=0.2223+1.0232*log(Kv at 100° C. in cSt); b) obtaining a secondsynthetic base stock lubricant, the second base stock lubricant has aviscosity less than 100 cSt, Kv100° C.; c) blending the first and secondbase stock lubricant to produce the lubricating oil.
 25. The lubricatingoil of claim 24 wherein the viscosity difference between the first andthe second base stocks is greater than 250 cSt, Kv100° C.
 26. Thelubricating oil of claim 24 wherein the high viscosity base stock is ametallocene catalyzed PAO base stock.
 27. The lubricating oil of claim24 wherein the second base stock is chosen from the group consisting ofGTL lubricants, wax derived lubricants, Poly Alpha Olefin, Brightstocks,Brightstocks with PIB, group I base stocks, Group II base stocks, GroupIII base stocks, Group V and any combination thereof.
 28. Thelubricating oil of claim 24 further comprising at least one additive,the additive chosen from the group consisting of antiwear, antioxidant,defoamant, demulsifier, detergent, dispersant, metal passivator,friction reducer, rust inhibitor, and any combination thereof.
 29. Thelubricating oil of claim 24 further comprising a third base stock. 30.The lubricating oil of claim 29, wherein the third base stock is chosenfrom a group consisting of a PAO with a viscosity of at least 1.5 cSt,Kv100° C. and no more than 100 cSt, Kv100° C., Group V base stock,including ester base stock, alkylated aromatic and any combinationthereof.
 31. The lubricating oil of claim 24 wherein the first basestock has a viscosity greater than 300 cSt, Kv100° C.
 32. Thelubricating oil of claim 24 further comprising at a third and fourthbase stock, the third base stock comprising a PAO having a viscosity ofat least 2 cSt and less than 60 cSt, Kv100° C., the fourth base stockcomprising an alkylated aromatic base stock.
 33. The lubricating oil ofclaim 24 wherein the second base stock has a viscosity greater than 1.5cSt and less than 40 cSt, Kv100° C.
 34. The lubricating oil of claim 24wherein the viscosity difference between the first base stock and thesecond base stock is greater than
 400. 35. The lubricating oil of claim24 wherein the first base stock has a molecular weight distribution lessthan algorithm:MWD=0.41667+0.725*log(Kv at 100° C. in cSt).